metal-organic compounds
Bis[N′-(2-pyridylmethylene-κN)benzohydrazide-κN′]bis(thiocyanato-κN)cobalt(II)
aNational Changhua University of Education, Department of Chemistry, Changhua, Taiwan 50058
*Correspondence e-mail: leehm@cc.ncue.edu.tw
In the title complex, [Co(NCS)2(C13H11N3O)2], the CoII centre adopts a distorted octahedral coordination geometry with two cis-bidentate Schiff base ligands and two cis thiocyanate ligands. The Schiff base ligand coordinates via the imine N and pyridine N atoms. The CoII atom lies on a crystallographic twofold rotational axis. Non-classical intermolecular C—H⋯O hydrogen bonds link the complex molecules into chains along [001].
Related literature
For metal complexes of the same Schiff base, see: Basak et al. (2008); Chen et al. (2005); Christidis et al. (1999); Pal & Pal (2002); Paschalidis & Gdaniec (2004); Paschalidis et al. (2000); Pelagatti et al. (2000); Pouralimardan et al. (2007); Ogata et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; 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: DIAMOND (Brandenburg, 1999).
Supporting information
10.1107/S1600536809029006/pv2186sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809029006/pv2186Isup2.hkl
To a methanolic solution (20 ml) of cobalt acetate tetrahydrate (0.249 g, 1.00 mmol), a solution of N'-(pyridin-2-ylmethylene)benzohydrazide (1.00 mmol) was added, followed by the addition with constant stirring of a solution of sodium thiocyanate (0.162 g, 2.00 mmol) in a minimum volume of water/methanol mixture. The resultant solution was kept at room temperature yielding orange crystals suitable for X-ray diffraction after a few days. Crystals of (I) were isolated by filtration and were air-dried.
All the H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 and N—H = 0.88 Å while Uiso(H) = 1.2Ueq(C or N) for all the H atoms.
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: DIAMOND (Brandenburg, 1999).[Co(NCS)2(C13H11N3O)2] | F(000) = 1284 |
Mr = 625.59 | Dx = 1.487 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2526 reflections |
a = 17.112 (10) Å | θ = 2.4–22.3° |
b = 10.256 (6) Å | µ = 0.81 mm−1 |
c = 17.945 (15) Å | T = 150 K |
β = 117.50 (3)° | Tubular, orange |
V = 2794 (3) Å3 | 0.19 × 0.18 × 0.10 mm |
Z = 4 |
Bruker SMART APEXII diffractometer | 2742 independent reflections |
Radiation source: fine-focus sealed tube | 1666 reflections with I > 2σ |
Graphite monochromator | Rint = 0.119 |
ω scans | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→21 |
Tmin = 0.862, Tmax = 0.924 | k = −12→12 |
15579 measured reflections | l = −22→22 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0417P)2] where P = (Fo2 + 2Fc2)/3 |
2742 reflections | (Δ/σ)max < 0.001 |
186 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
[Co(NCS)2(C13H11N3O)2] | V = 2794 (3) Å3 |
Mr = 625.59 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.112 (10) Å | µ = 0.81 mm−1 |
b = 10.256 (6) Å | T = 150 K |
c = 17.945 (15) Å | 0.19 × 0.18 × 0.10 mm |
β = 117.50 (3)° |
Bruker SMART APEXII diffractometer | 2742 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1666 reflections with I > 2σ |
Tmin = 0.862, Tmax = 0.924 | Rint = 0.119 |
15579 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.60 e Å−3 |
2742 reflections | Δρmin = −0.55 e Å−3 |
186 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.0000 | 0.87355 (6) | 0.2500 | 0.0423 (2) | |
S1 | −0.23413 (6) | 0.57257 (9) | 0.08021 (6) | 0.0655 (3) | |
O1 | 0.08519 (16) | 0.8442 (2) | 0.02024 (13) | 0.0694 (7) | |
N1 | −0.00183 (16) | 0.8085 (3) | 0.08164 (14) | 0.0517 (7) | |
H1A | −0.0481 | 0.7640 | 0.0762 | 0.062* | |
N2 | 0.03351 (16) | 0.8912 (2) | 0.14860 (13) | 0.0429 (6) | |
N3 | 0.09438 (15) | 1.0297 (2) | 0.28764 (13) | 0.0416 (6) | |
N4 | −0.09755 (18) | 0.7417 (3) | 0.18238 (16) | 0.0555 (7) | |
C1 | −0.1101 (2) | 0.6416 (3) | −0.05536 (17) | 0.0510 (8) | |
H1 | −0.1368 | 0.6775 | −0.0239 | 0.061* | |
C2 | −0.1537 (2) | 0.5487 (4) | −0.1162 (2) | 0.0620 (10) | |
H2 | −0.2110 | 0.5218 | −0.1269 | 0.074* | |
C3 | −0.1155 (3) | 0.4944 (4) | −0.1620 (2) | 0.0651 (10) | |
H3 | −0.1463 | 0.4302 | −0.2034 | 0.078* | |
C4 | −0.0334 (2) | 0.5333 (4) | −0.1474 (2) | 0.0610 (10) | |
H4 | −0.0070 | 0.4963 | −0.1788 | 0.073* | |
C5 | 0.0115 (2) | 0.6270 (3) | −0.08666 (18) | 0.0532 (9) | |
H5 | 0.0687 | 0.6536 | −0.0768 | 0.064* | |
C6 | −0.0261 (2) | 0.6823 (3) | −0.04033 (16) | 0.0419 (7) | |
C7 | 0.0246 (2) | 0.7850 (3) | 0.02159 (17) | 0.0451 (8) | |
C8 | 0.0888 (2) | 0.9814 (3) | 0.15504 (16) | 0.0428 (7) | |
H8 | 0.1071 | 0.9942 | 0.1130 | 0.051* | |
C9 | 0.12177 (18) | 1.0627 (3) | 0.23016 (16) | 0.0391 (7) | |
C10 | 0.1779 (2) | 1.1670 (3) | 0.24127 (18) | 0.0495 (8) | |
H10 | 0.1959 | 1.1867 | 0.1998 | 0.059* | |
C11 | 0.2070 (2) | 1.2413 (3) | 0.3128 (2) | 0.0588 (9) | |
H11 | 0.2442 | 1.3145 | 0.3210 | 0.071* | |
C12 | 0.1812 (2) | 1.2073 (4) | 0.3725 (2) | 0.0627 (10) | |
H12 | 0.2013 | 1.2560 | 0.4230 | 0.075* | |
C13 | 0.1256 (2) | 1.1012 (3) | 0.35803 (18) | 0.0527 (9) | |
H13 | 0.1089 | 1.0783 | 0.4000 | 0.063* | |
C14 | −0.1556 (2) | 0.6713 (3) | 0.13930 (19) | 0.0472 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0530 (4) | 0.0434 (4) | 0.0368 (3) | 0.000 | 0.0260 (3) | 0.000 |
S1 | 0.0679 (7) | 0.0601 (6) | 0.0712 (6) | −0.0156 (5) | 0.0344 (5) | −0.0118 (5) |
O1 | 0.0732 (17) | 0.093 (2) | 0.0596 (13) | −0.0341 (16) | 0.0455 (13) | −0.0249 (14) |
N1 | 0.0644 (18) | 0.0570 (18) | 0.0456 (13) | −0.0208 (15) | 0.0355 (13) | −0.0168 (14) |
N2 | 0.0544 (17) | 0.0446 (16) | 0.0325 (12) | −0.0039 (14) | 0.0225 (12) | −0.0067 (13) |
N3 | 0.0454 (15) | 0.0473 (16) | 0.0335 (12) | 0.0040 (13) | 0.0196 (11) | −0.0042 (12) |
N4 | 0.0649 (19) | 0.0545 (19) | 0.0543 (15) | −0.0096 (17) | 0.0336 (15) | −0.0041 (16) |
C1 | 0.055 (2) | 0.059 (2) | 0.0415 (15) | −0.0055 (19) | 0.0240 (15) | −0.0068 (17) |
C2 | 0.057 (2) | 0.072 (3) | 0.0566 (19) | −0.017 (2) | 0.0256 (18) | −0.015 (2) |
C3 | 0.075 (3) | 0.063 (3) | 0.0542 (19) | −0.008 (2) | 0.028 (2) | −0.017 (2) |
C4 | 0.075 (3) | 0.063 (2) | 0.0526 (19) | 0.000 (2) | 0.0364 (19) | −0.013 (2) |
C5 | 0.057 (2) | 0.064 (2) | 0.0481 (17) | −0.0047 (19) | 0.0329 (17) | −0.0077 (19) |
C6 | 0.0475 (19) | 0.0446 (19) | 0.0324 (14) | −0.0012 (17) | 0.0173 (14) | −0.0009 (15) |
C7 | 0.053 (2) | 0.049 (2) | 0.0381 (15) | 0.0017 (18) | 0.0249 (15) | 0.0019 (16) |
C8 | 0.0485 (19) | 0.0461 (19) | 0.0376 (15) | −0.0008 (17) | 0.0231 (14) | −0.0006 (15) |
C9 | 0.0389 (18) | 0.0405 (19) | 0.0362 (14) | 0.0056 (16) | 0.0160 (14) | 0.0004 (14) |
C10 | 0.053 (2) | 0.046 (2) | 0.0452 (16) | −0.0013 (18) | 0.0194 (16) | 0.0016 (17) |
C11 | 0.055 (2) | 0.051 (2) | 0.0608 (19) | −0.0083 (19) | 0.0193 (17) | −0.008 (2) |
C12 | 0.061 (2) | 0.063 (3) | 0.0556 (19) | −0.006 (2) | 0.0192 (18) | −0.027 (2) |
C13 | 0.055 (2) | 0.059 (2) | 0.0439 (16) | 0.0025 (19) | 0.0236 (16) | −0.0093 (18) |
C14 | 0.056 (2) | 0.044 (2) | 0.0516 (18) | −0.0009 (18) | 0.0335 (17) | 0.0049 (17) |
Co1—N4i | 2.054 (3) | C2—H2 | 0.9500 |
Co1—N4 | 2.054 (3) | C3—C4 | 1.364 (4) |
Co1—N3 | 2.150 (3) | C3—H3 | 0.9500 |
Co1—N3i | 2.150 (3) | C4—C5 | 1.389 (4) |
Co1—N2 | 2.153 (3) | C4—H4 | 0.9500 |
Co1—N2i | 2.153 (3) | C5—C6 | 1.386 (4) |
S1—C14 | 1.624 (4) | C5—H5 | 0.9500 |
O1—C7 | 1.211 (3) | C6—C7 | 1.486 (4) |
N1—N2 | 1.363 (3) | C8—C9 | 1.459 (4) |
N1—C7 | 1.369 (3) | C8—H8 | 0.9500 |
N1—H1A | 0.8801 | C9—C10 | 1.389 (4) |
N2—C8 | 1.289 (4) | C10—C11 | 1.373 (4) |
N3—C13 | 1.340 (3) | C10—H10 | 0.9500 |
N3—C9 | 1.358 (3) | C11—C12 | 1.379 (4) |
N4—C14 | 1.182 (4) | C11—H11 | 0.9500 |
C1—C2 | 1.380 (4) | C12—C13 | 1.389 (4) |
C1—C6 | 1.397 (4) | C12—H12 | 0.9500 |
C1—H1 | 0.9500 | C13—H13 | 0.9500 |
C2—C3 | 1.381 (4) | ||
N4i—Co1—N4 | 97.62 (16) | C2—C3—H3 | 120.1 |
N4i—Co1—N3 | 90.99 (11) | C3—C4—C5 | 120.1 (3) |
N4—Co1—N3 | 164.56 (8) | C3—C4—H4 | 120.0 |
N4i—Co1—N3i | 164.56 (8) | C5—C4—H4 | 120.0 |
N4—Co1—N3i | 90.99 (11) | C4—C5—C6 | 120.7 (3) |
N3—Co1—N3i | 83.68 (13) | C4—C5—H5 | 119.6 |
N4i—Co1—N2 | 95.39 (10) | C6—C5—H5 | 119.6 |
N4—Co1—N2 | 90.98 (10) | C5—C6—C1 | 118.9 (3) |
N3—Co1—N2 | 75.41 (9) | C5—C6—C7 | 117.7 (3) |
N3i—Co1—N2 | 97.25 (9) | C1—C6—C7 | 123.3 (3) |
N4i—Co1—N2i | 90.98 (10) | O1—C7—N1 | 121.6 (3) |
N4—Co1—N2i | 95.39 (10) | O1—C7—C6 | 123.4 (2) |
N3—Co1—N2i | 97.25 (9) | N1—C7—C6 | 115.0 (3) |
N3i—Co1—N2i | 75.41 (9) | N2—C8—C9 | 116.6 (2) |
N2—Co1—N2i | 170.33 (14) | N2—C8—H8 | 121.7 |
N2—N1—C7 | 129.1 (2) | C9—C8—H8 | 121.7 |
N2—N1—H1A | 115.5 | N3—C9—C10 | 122.7 (3) |
C7—N1—H1A | 115.4 | N3—C9—C8 | 116.0 (3) |
C8—N2—N1 | 122.3 (2) | C10—C9—C8 | 121.3 (3) |
C8—N2—Co1 | 117.08 (18) | C11—C10—C9 | 119.4 (3) |
N1—N2—Co1 | 120.63 (18) | C11—C10—H10 | 120.3 |
C13—N3—C9 | 116.9 (3) | C9—C10—H10 | 120.3 |
C13—N3—Co1 | 128.18 (19) | C10—C11—C12 | 118.5 (3) |
C9—N3—Co1 | 114.80 (18) | C10—C11—H11 | 120.7 |
C14—N4—Co1 | 175.8 (2) | C12—C11—H11 | 120.7 |
C2—C1—C6 | 119.4 (3) | C11—C12—C13 | 119.4 (3) |
C2—C1—H1 | 120.3 | C11—C12—H12 | 120.3 |
C6—C1—H1 | 120.3 | C13—C12—H12 | 120.3 |
C1—C2—C3 | 121.2 (3) | N3—C13—C12 | 123.0 (3) |
C1—C2—H2 | 119.4 | N3—C13—H13 | 118.5 |
C3—C2—H2 | 119.4 | C12—C13—H13 | 118.5 |
C4—C3—C2 | 119.7 (3) | N4—C14—S1 | 179.0 (3) |
C4—C3—H3 | 120.1 | ||
C7—N1—N2—C8 | 14.7 (5) | C4—C5—C6—C7 | −178.0 (3) |
C7—N1—N2—Co1 | −164.3 (2) | C2—C1—C6—C5 | −0.6 (4) |
N4i—Co1—N2—C8 | −90.9 (2) | C2—C1—C6—C7 | 177.7 (3) |
N4—Co1—N2—C8 | 171.3 (2) | N2—N1—C7—O1 | −3.1 (5) |
N3—Co1—N2—C8 | −1.3 (2) | N2—N1—C7—C6 | 176.6 (3) |
N3i—Co1—N2—C8 | 80.2 (2) | C5—C6—C7—O1 | 18.1 (4) |
N4i—Co1—N2—N1 | 88.1 (2) | C1—C6—C7—O1 | −160.3 (3) |
N4—Co1—N2—N1 | −9.6 (2) | C5—C6—C7—N1 | −161.6 (3) |
N3—Co1—N2—N1 | 177.7 (2) | C1—C6—C7—N1 | 20.1 (4) |
N3i—Co1—N2—N1 | −100.8 (2) | N1—N2—C8—C9 | −179.7 (2) |
N4i—Co1—N3—C13 | −85.0 (3) | Co1—N2—C8—C9 | −0.7 (3) |
N4—Co1—N3—C13 | 150.9 (3) | C13—N3—C9—C10 | −1.4 (4) |
N3i—Co1—N3—C13 | 80.5 (2) | Co1—N3—C9—C10 | 175.5 (2) |
N2—Co1—N3—C13 | 179.7 (3) | C13—N3—C9—C8 | 178.4 (3) |
N2i—Co1—N3—C13 | 6.1 (3) | Co1—N3—C9—C8 | −4.6 (3) |
N4i—Co1—N3—C9 | 98.5 (2) | N2—C8—C9—N3 | 3.6 (4) |
N4—Co1—N3—C9 | −25.7 (5) | N2—C8—C9—C10 | −176.5 (3) |
N3i—Co1—N3—C9 | −96.0 (2) | N3—C9—C10—C11 | −0.4 (5) |
N2—Co1—N3—C9 | 3.18 (19) | C8—C9—C10—C11 | 179.7 (3) |
N2i—Co1—N3—C9 | −170.40 (19) | C9—C10—C11—C12 | 1.7 (5) |
C6—C1—C2—C3 | 0.7 (5) | C10—C11—C12—C13 | −1.2 (5) |
C1—C2—C3—C4 | −0.4 (5) | C9—N3—C13—C12 | 2.0 (4) |
C2—C3—C4—C5 | 0.1 (5) | Co1—N3—C13—C12 | −174.5 (2) |
C3—C4—C5—C6 | −0.1 (5) | C11—C12—C13—N3 | −0.8 (5) |
C4—C5—C6—C1 | 0.3 (5) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O1ii | 0.95 | 2.50 | 3.335 (5) | 146 |
Symmetry code: (ii) x, −y+2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(NCS)2(C13H11N3O)2] |
Mr | 625.59 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 17.112 (10), 10.256 (6), 17.945 (15) |
β (°) | 117.50 (3) |
V (Å3) | 2794 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.19 × 0.18 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.862, 0.924 |
No. of measured, independent and observed (I > 2σ) reflections | 15579, 2742, 1666 |
Rint | 0.119 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.100, 0.97 |
No. of reflections | 2742 |
No. of parameters | 186 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.55 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O1i | 0.95 | 2.50 | 3.335 (5) | 146 |
Symmetry code: (i) x, −y+2, z+1/2. |
Acknowledgements
We are grateful to the National Science Council of Taiwan for financial support.
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 Schiff base, N'-(pyridin-2-ylmethylene)benzohydrazide, reacts with cobalt acetate tetrahydrate and sodium thiocyanate in water/methanol mixture to afford the tilte complex, (I). The cobalt atom lies on a crystallographic 2-fold rotational axis. The complex (I) adopts octahedral coordination geometry with the two bidentate Schiff base ligands being cis to each other (Fig. 1). The Schiff base coordinates via the imine N and pyridine N atoms. The two thiocyanate ligands are also cis to each other.
Metal complexes of the same Schiff base ligand have been reported in the literature (Basak et al. 2008; Chen et al. 2005; Christidis, et al. 1999; Pal & Pal, 2002; Paschalidis & Gdaniec, 2004; Paschalidis et al. 2000; Pelagatti et al. 2000; Pouralimardan, et al. 2007; Ogata et al. 2008).
Non-classical intermolecular H-bonds of the type C—H···O exist (Table 1). These H-bonds link the complex into one-dimensional hydrogen bonded chains (Fig. 2).