metal-organic compounds
Poly[(μ3-pyridine-4-carboxylato-κ3O:O′:N)(pyridin-1-ium-4-carboxylato-κO)(thiocyanato-κN)cobalt(II)]
aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: cnaether@ac.uni-kiel.de
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.
Related literature
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
Crystal data
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Refinement
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Data collection: X-AREA (Stoe & Cie, 2008); cell 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: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812044431/wm2684sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044431/wm2684Isup2.hkl
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.
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.
Data collection: X-AREA (Stoe & Cie, 2008); cell
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).[Co(C6H5NO2)(NCS)(C6H4NO2)] | F(000) = 732 |
Mr = 362.22 | Dx = 1.665 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 12489 reflections |
a = 8.7857 (7) Å | θ = 2.3–26.0° |
b = 13.5401 (8) Å | µ = 1.35 mm−1 |
c = 12.2054 (9) Å | T = 293 K |
β = 95.740 (6)° | Block, pink |
V = 1444.67 (18) Å3 | 0.18 × 0.13 × 0.04 mm |
Z = 4 |
Stoe IPDS-2 diffractometer | 2844 independent reflections |
Radiation source: fine-focus sealed tube | 2353 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) | h = −9→10 |
Tmin = 0.808, Tmax = 0.954 | k = −16→16 |
12489 measured reflections | l = −15→15 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-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 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
[Co(C6H5NO2)(NCS)(C6H4NO2)] | V = 1444.67 (18) Å3 |
Mr = 362.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.7857 (7) Å | µ = 1.35 mm−1 |
b = 13.5401 (8) Å | T = 293 K |
c = 12.2054 (9) Å | 0.18 × 0.13 × 0.04 mm |
β = 95.740 (6)° |
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 = 0.954 | Rint = 0.041 |
12489 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.46 e Å−3 |
2844 reflections | Δρmin = −0.39 e Å−3 |
199 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.55767 (5) | 0.54579 (3) | 0.37683 (3) | 0.04212 (15) | |
N1 | 0.6768 (4) | 0.5335 (2) | 0.2453 (3) | 0.0650 (8) | |
C1 | 0.7529 (4) | 0.5189 (3) | 0.1751 (3) | 0.0569 (9) | |
S1 | 0.85857 (16) | 0.50015 (10) | 0.07668 (11) | 0.0870 (4) | |
O11 | 0.7180 (4) | 0.3217 (2) | 0.3482 (2) | 0.0961 (12) | |
N11 | 1.0561 (4) | 0.2118 (2) | 0.6656 (2) | 0.0602 (8) | |
H1N | 1.1155 | 0.1797 | 0.7133 | 0.072* | |
C11 | 1.0285 (5) | 0.3058 (3) | 0.6833 (3) | 0.0691 (11) | |
H11 | 1.0737 | 0.3363 | 0.7467 | 0.083* | |
O12 | 0.7060 (4) | 0.44642 (18) | 0.4654 (2) | 0.0746 (9) | |
C12 | 0.9336 (5) | 0.3592 (3) | 0.6092 (3) | 0.0626 (10) | |
H12 | 0.9141 | 0.4255 | 0.6219 | 0.075* | |
C13 | 0.8682 (4) | 0.3134 (2) | 0.5164 (3) | 0.0472 (8) | |
C14 | 0.9021 (6) | 0.2159 (3) | 0.4995 (3) | 0.0731 (13) | |
H14 | 0.8619 | 0.1840 | 0.4356 | 0.088* | |
C15 | 0.9951 (6) | 0.1659 (3) | 0.5768 (3) | 0.0797 (14) | |
H15 | 1.0155 | 0.0993 | 0.5667 | 0.096* | |
C16 | 0.7540 (5) | 0.3656 (3) | 0.4352 (3) | 0.0585 (10) | |
N21 | 0.0790 (3) | 0.15794 (17) | 0.20950 (19) | 0.0409 (6) | |
C21 | 0.1656 (4) | 0.1340 (2) | 0.3023 (3) | 0.0541 (9) | |
H21 | 0.1687 | 0.0682 | 0.3243 | 0.065* | |
O21 | 0.3758 (3) | 0.35997 (15) | 0.50108 (16) | 0.0480 (5) | |
O22 | 0.3902 (3) | 0.44629 (15) | 0.34512 (17) | 0.0468 (5) | |
C22 | 0.2501 (4) | 0.2017 (2) | 0.3666 (3) | 0.0525 (9) | |
H22 | 0.3069 | 0.1817 | 0.4311 | 0.063* | |
C23 | 0.2502 (4) | 0.2995 (2) | 0.3350 (2) | 0.0392 (7) | |
C24 | 0.1599 (4) | 0.3245 (2) | 0.2392 (3) | 0.0520 (8) | |
H24 | 0.1560 | 0.3896 | 0.2146 | 0.062* | |
C25 | 0.0765 (4) | 0.2528 (2) | 0.1808 (3) | 0.0503 (8) | |
H25 | 0.0149 | 0.2714 | 0.1177 | 0.060* | |
C26 | 0.3462 (4) | 0.3749 (2) | 0.3992 (2) | 0.0397 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0532 (3) | 0.0318 (2) | 0.0380 (2) | −0.00216 (19) | −0.01220 (16) | −0.00046 (16) |
N1 | 0.061 (2) | 0.0587 (18) | 0.076 (2) | 0.0046 (16) | 0.0107 (17) | −0.0018 (16) |
C1 | 0.055 (2) | 0.0454 (18) | 0.070 (2) | −0.0019 (16) | 0.0022 (19) | −0.0096 (16) |
S1 | 0.0904 (9) | 0.0886 (8) | 0.0864 (8) | −0.0032 (7) | 0.0312 (7) | −0.0235 (7) |
O11 | 0.144 (3) | 0.0572 (16) | 0.0716 (18) | 0.0320 (18) | −0.066 (2) | −0.0231 (14) |
N11 | 0.0593 (19) | 0.0640 (19) | 0.0532 (17) | 0.0088 (15) | −0.0147 (14) | 0.0118 (14) |
C11 | 0.078 (3) | 0.066 (2) | 0.056 (2) | −0.016 (2) | −0.031 (2) | 0.0079 (18) |
O12 | 0.100 (2) | 0.0499 (14) | 0.0645 (15) | 0.0289 (14) | −0.0373 (15) | −0.0134 (12) |
C12 | 0.077 (3) | 0.0465 (18) | 0.058 (2) | −0.0028 (18) | −0.0265 (19) | −0.0022 (15) |
C13 | 0.0520 (19) | 0.0437 (16) | 0.0430 (16) | 0.0054 (14) | −0.0095 (14) | −0.0023 (13) |
C14 | 0.105 (3) | 0.057 (2) | 0.049 (2) | 0.030 (2) | −0.031 (2) | −0.0147 (17) |
C15 | 0.109 (4) | 0.063 (2) | 0.061 (2) | 0.037 (2) | −0.023 (2) | −0.0084 (19) |
C16 | 0.072 (2) | 0.0440 (18) | 0.0532 (19) | 0.0084 (17) | −0.0277 (17) | −0.0045 (15) |
N21 | 0.0492 (15) | 0.0369 (13) | 0.0350 (12) | −0.0022 (11) | −0.0040 (11) | −0.0004 (10) |
C21 | 0.080 (2) | 0.0332 (15) | 0.0446 (17) | −0.0082 (15) | −0.0168 (16) | 0.0043 (13) |
O21 | 0.0702 (15) | 0.0338 (10) | 0.0367 (11) | −0.0032 (10) | −0.0108 (10) | −0.0008 (8) |
O22 | 0.0565 (13) | 0.0368 (11) | 0.0444 (11) | −0.0065 (10) | −0.0086 (10) | 0.0029 (9) |
C22 | 0.076 (2) | 0.0396 (16) | 0.0373 (15) | −0.0055 (16) | −0.0168 (15) | 0.0026 (12) |
C23 | 0.0497 (18) | 0.0340 (14) | 0.0324 (14) | −0.0022 (13) | −0.0037 (13) | −0.0027 (11) |
C24 | 0.066 (2) | 0.0332 (15) | 0.0518 (18) | −0.0011 (14) | −0.0194 (16) | 0.0025 (13) |
C25 | 0.063 (2) | 0.0376 (16) | 0.0458 (17) | 0.0009 (15) | −0.0183 (15) | −0.0002 (13) |
C26 | 0.0462 (17) | 0.0309 (14) | 0.0402 (15) | 0.0021 (12) | −0.0054 (13) | −0.0014 (11) |
Co1—O22 | 2.004 (2) | C14—C15 | 1.364 (5) |
Co1—O21i | 2.004 (2) | C14—H14 | 0.9300 |
Co1—N1 | 2.010 (4) | C15—H15 | 0.9300 |
Co1—O12 | 2.097 (2) | N21—C25 | 1.331 (4) |
Co1—N21ii | 2.146 (2) | N21—C21 | 1.339 (4) |
N1—C1 | 1.155 (5) | N21—Co1iii | 2.146 (2) |
C1—S1 | 1.610 (4) | C21—C22 | 1.376 (4) |
O11—C16 | 1.230 (4) | C21—H21 | 0.9300 |
N11—C15 | 1.316 (5) | O21—C26 | 1.261 (3) |
N11—C11 | 1.318 (5) | O21—Co1i | 2.004 (2) |
N11—H1N | 0.8600 | O22—C26 | 1.253 (3) |
C11—C12 | 1.373 (5) | C22—C23 | 1.379 (4) |
C11—H11 | 0.9300 | C22—H22 | 0.9300 |
O12—C16 | 1.242 (4) | C23—C24 | 1.388 (4) |
C12—C13 | 1.366 (4) | C23—C26 | 1.495 (4) |
C12—H12 | 0.9300 | C24—C25 | 1.373 (4) |
C13—C14 | 1.374 (5) | C24—H24 | 0.9300 |
C13—C16 | 1.514 (4) | C25—H25 | 0.9300 |
O22—Co1—O21i | 136.53 (10) | N11—C15—H15 | 119.9 |
O22—Co1—N1 | 102.78 (12) | C14—C15—H15 | 119.9 |
O21i—Co1—N1 | 120.67 (12) | O11—C16—O12 | 128.1 (3) |
O22—Co1—O12 | 94.28 (10) | O11—C16—C13 | 115.8 (3) |
O21i—Co1—O12 | 84.54 (9) | O12—C16—C13 | 116.0 (3) |
N1—Co1—O12 | 90.72 (13) | C25—N21—C21 | 116.7 (3) |
O22—Co1—N21ii | 90.97 (9) | C25—N21—Co1iii | 124.0 (2) |
O21i—Co1—N21ii | 91.26 (9) | C21—N21—Co1iii | 119.1 (2) |
N1—Co1—N21ii | 88.66 (12) | N21—C21—C22 | 123.3 (3) |
O12—Co1—N21ii | 174.71 (11) | N21—C21—H21 | 118.3 |
C1—N1—Co1 | 173.2 (3) | C22—C21—H21 | 118.3 |
N1—C1—S1 | 179.2 (4) | C26—O21—Co1i | 130.33 (18) |
C15—N11—C11 | 121.6 (3) | C26—O22—Co1 | 132.53 (19) |
C15—N11—H1N | 119.2 | C21—C22—C23 | 119.7 (3) |
C11—N11—H1N | 119.2 | C21—C22—H22 | 120.1 |
N11—C11—C12 | 120.6 (3) | C23—C22—H22 | 120.1 |
N11—C11—H11 | 119.7 | C22—C23—C24 | 117.0 (3) |
C12—C11—H11 | 119.7 | C22—C23—C26 | 121.7 (3) |
C16—O12—Co1 | 128.6 (2) | C24—C23—C26 | 121.4 (3) |
C13—C12—C11 | 119.0 (3) | C25—C24—C23 | 119.7 (3) |
C13—C12—H12 | 120.5 | C25—C24—H24 | 120.2 |
C11—C12—H12 | 120.5 | C23—C24—H24 | 120.2 |
C12—C13—C14 | 118.7 (3) | N21—C25—C24 | 123.5 (3) |
C12—C13—C16 | 121.8 (3) | N21—C25—H25 | 118.2 |
C14—C13—C16 | 119.4 (3) | C24—C25—H25 | 118.2 |
C15—C14—C13 | 119.8 (3) | O22—C26—O21 | 126.8 (3) |
C15—C14—H14 | 120.1 | O22—C26—C23 | 116.0 (2) |
C13—C14—H14 | 120.1 | O21—C26—C23 | 117.2 (3) |
N11—C15—C14 | 120.1 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H1N···O11iv | 0.86 | 1.80 | 2.561 (4) | 147 |
Symmetry code: (iv) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C6H5NO2)(NCS)(C6H4NO2)] |
Mr | 362.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.7857 (7), 13.5401 (8), 12.2054 (9) |
β (°) | 95.740 (6) |
V (Å3) | 1444.67 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.35 |
Crystal size (mm) | 0.18 × 0.13 × 0.04 |
Data collection | |
Diffractometer | Stoe IPDS2 diffractometer |
Absorption correction | Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) |
Tmin, Tmax | 0.808, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12489, 2844, 2353 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.098, 1.13 |
No. of reflections | 2844 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.39 |
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), publCIF (Westrip, 2010).
Co1—O22 | 2.004 (2) | Co1—O12 | 2.097 (2) |
Co1—O21i | 2.004 (2) | Co1—N21ii | 2.146 (2) |
Co1—N1 | 2.010 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H1N···O11iii | 0.86 | 1.80 | 2.561 (4) | 147.1 |
Symmetry code: (iii) x+1/2, −y+1/2, z+1/2. |
Acknowledgements
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
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.