metal-organic compounds
trans-(Pyrimidine-2-thiolato-κ2N,S)[tris(2-aminoethyl)amine-κ4N,N′,N′′,N′′′]cobalt(III) chloride hexafluoridophosphate
aDepartment of Applied Science, Faculty of Science, Kochi University, Akebono-cho, Kochi 780-8520, Japan
*Correspondence e-mail: yonemura@kochi-u.ac.jp
In the title compound, [Co(C4H3N2S)(C6H18N4)](Cl)PF6, the CoIII ion is coordinated by a tripod-like tetradentate ligand and a monoanionic N,S-bidentate ligand in an approximately octahedral CoN4OS geometry. The anionic S atom of the pyrimidine-2-thiolate (pymt) ligand is coordinated in the trans position to the primary amine N atom (Nprim) of the tris(2-aminoethyl)amine (tren) ligand. The exhibits short intermolecular N—H⋯N hydrogen bonds (N⋯N <3.2 Å), and intermolecular N—H⋯Cl and C—H⋯F contacts, leading to the formation of an infinite two-dimensional network.
Related literature
For the synthesis and chemistry of similar tren [tren = tris(2-aminoethyl)amine] complexes, see: Jackson & Sargeson (1978); Kojima et al. (1994); Mitsui et al. (1976); Ohba & Saito (1984); Okamoto et al. (1990); Yonemura et al. (1997).
Experimental
Crystal data
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Refinement
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Data collection: WinAFC (Rigaku/MSC, 2000); cell WinAFC; data reduction: CrystalStructure (Rigaku/MSC, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.
Supporting information
10.1107/S1600536809032395/su2138sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809032395/su2138Isup2.hkl
A methanolic solution of 2-pyrimidinethiol (1.12 g, 10 mmol) was adjusted to pH 8.0 with aqueous solutions of NaOH and HCl. The mixed solution was added to an aqueous solution of [CoCl2(tren)]Cl (3.11 g, 10 mmol) and stirred at 40 °C for 1 h. The reaction mixture was poured onto an SP-Sepahadex C-25 column (Na+ form, 7 cm × 7 cm) and the adsorbed band was developed with a 0.2 mol dm-3 NaCl aqueous solution. The eluted red band was concentrated to a small volume, the precipitated NaCl was filtered off and the red filtrate was added to a solution of NH4PF6 (1.1 g, 6.7 mmol). The resulting red powder was collected by filtration and recrystallized from water. A few days later red crystals of the title compoun were obtained with a yield of 1.50 g (35%). Anal. Calc. for [Co(pymt)(tren)]ClPF6 = C10H21CoN6SClPF6: C 24.18, H 4.26, N 16.92%, Found: C 24.09, H 4.24, N 17.04%.
The H-atoms were included in calculated positions and treated as riding atoms: N—H = 0.90 Å, C—H = 0.93–0.97 Å, with Uiso(H) = 1.2Ueq(C,N).
Data collection: WinAFC (Rigaku/MSC, 2000); cell
WinAFC (Rigaku/MSC, 2000); data reduction: CrystalStructure (Rigaku/MSC, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2007).Fig. 1. A view of the molecular structure of the title compound, showing the atom-labelling scheme and 50% probability displacement ellipsoids. | |
Fig. 2. A view along the b-axis of the crystal packing diagram of the title compound, showing the N–H···N hydrogen-bonds and N–H···Cl and C–H···F contacts as dashed lines (the H-atoms have been omitted for clarity). |
[Co(C4H3N2S)(C6H18N4)](Cl)PF6 | F(000) = 1008.0 |
Mr = 496.73 | Dx = 1.747 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 12.7106 (17) Å | θ = 15.4–17.1° |
b = 11.326 (2) Å | µ = 1.31 mm−1 |
c = 14.205 (2) Å | T = 296 K |
β = 112.549 (10)° | Prismatic, red-brown |
V = 1888.7 (5) Å3 | 0.45 × 0.35 × 0.20 mm |
Z = 4 |
Rigaku AFC-7S diffractometer | Rint = 0.031 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = −16→15 |
Tmin = 0.503, Tmax = 0.770 | k = −14→0 |
5201 measured reflections | l = −10→18 |
4342 independent reflections | 3 standard reflections every 150 reflections |
3416 reflections with F2 > 2σ(F2) | intensity decay: 5.4% |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.057 | w = 1/[σ2(Fo2) + (0.1106P)2 + 1.816P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.174 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 1.14 e Å−3 |
4342 reflections | Δρmin = −0.87 e Å−3 |
237 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008) |
0 restraints | Extinction coefficient: 0.0077 (13) |
[Co(C4H3N2S)(C6H18N4)](Cl)PF6 | V = 1888.7 (5) Å3 |
Mr = 496.73 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7106 (17) Å | µ = 1.31 mm−1 |
b = 11.326 (2) Å | T = 296 K |
c = 14.205 (2) Å | 0.45 × 0.35 × 0.20 mm |
β = 112.549 (10)° |
Rigaku AFC-7S diffractometer | 3416 reflections with F2 > 2σ(F2) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.031 |
Tmin = 0.503, Tmax = 0.770 | 3 standard reflections every 150 reflections |
5201 measured reflections | intensity decay: 5.4% |
4342 independent reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.174 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.14 e Å−3 |
4342 reflections | Δρmin = −0.87 e Å−3 |
237 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.18778 (4) | 0.70419 (4) | 0.19018 (3) | 0.0308 (1) | |
S1 | 0.23158 (8) | 0.80886 (9) | 0.06968 (7) | 0.0410 (3) | |
N1 | 0.0476 (2) | 0.7685 (3) | 0.0930 (2) | 0.0372 (9) | |
N2 | 0.0184 (3) | 0.8748 (3) | −0.0597 (2) | 0.0470 (10) | |
N3 | 0.3357 (2) | 0.6418 (3) | 0.2771 (2) | 0.0385 (8) | |
N4 | 0.1255 (2) | 0.6241 (3) | 0.2792 (2) | 0.0406 (9) | |
N5 | 0.1706 (2) | 0.5600 (3) | 0.1086 (2) | 0.0405 (9) | |
N6 | 0.2288 (2) | 0.8465 (3) | 0.2764 (2) | 0.0410 (9) | |
C1 | 0.0848 (3) | 0.8230 (3) | 0.0267 (2) | 0.0384 (10) | |
C2 | −0.0930 (4) | 0.8686 (4) | −0.0804 (3) | 0.0548 (12) | |
C3 | −0.1387 (3) | 0.8134 (4) | −0.0174 (3) | 0.0568 (14) | |
C4 | −0.0639 (3) | 0.7636 (4) | 0.0716 (3) | 0.0488 (12) | |
C5 | 0.3252 (3) | 0.5685 (3) | 0.3615 (2) | 0.0452 (11) | |
C6 | 0.2038 (3) | 0.5283 (3) | 0.3347 (2) | 0.0438 (11) | |
C7 | 0.3755 (3) | 0.5708 (4) | 0.2084 (3) | 0.0508 (12) | |
C8 | 0.2801 (4) | 0.4922 (4) | 0.1429 (3) | 0.0516 (12) | |
C9 | 0.4102 (3) | 0.7457 (4) | 0.3219 (3) | 0.0484 (11) | |
C10 | 0.3430 (3) | 0.8304 (3) | 0.3597 (3) | 0.0493 (12) | |
P1 | 0.35869 (9) | 0.19313 (10) | 0.36387 (9) | 0.0445 (3) | |
F1 | 0.2435 (3) | 0.2566 (4) | 0.2930 (3) | 0.1068 (16) | |
F2 | 0.4274 (5) | 0.2804 (3) | 0.3247 (6) | 0.142 (3) | |
F3 | 0.3517 (3) | 0.1030 (3) | 0.2757 (2) | 0.0873 (12) | |
F4 | 0.4707 (3) | 0.1283 (5) | 0.4302 (3) | 0.1148 (16) | |
F5 | 0.2846 (5) | 0.1060 (4) | 0.3963 (5) | 0.147 (3) | |
F6 | 0.3610 (4) | 0.2851 (4) | 0.4487 (3) | 0.1020 (16) | |
Cl1 | 0.03840 (9) | 0.91504 (11) | 0.36135 (8) | 0.0531 (3) | |
H1 | −0.14280 | 0.90310 | −0.14030 | 0.0660* | |
H2 | −0.21700 | 0.81010 | −0.03460 | 0.0680* | |
H3 | −0.09110 | 0.72690 | 0.11630 | 0.0590* | |
H4 | 0.34970 | 0.61460 | 0.42370 | 0.0540* | |
H5 | 0.37450 | 0.50000 | 0.37360 | 0.0540* | |
H6 | 0.18900 | 0.45820 | 0.29230 | 0.0530* | |
H7 | 0.19180 | 0.50880 | 0.39630 | 0.0530* | |
H8 | 0.11730 | 0.67600 | 0.32400 | 0.0490* | |
H9 | 0.05650 | 0.59400 | 0.24190 | 0.0490* | |
H10 | 0.44060 | 0.52320 | 0.24880 | 0.0610* | |
H11 | 0.39870 | 0.62300 | 0.16570 | 0.0610* | |
H12 | 0.29470 | 0.46570 | 0.08420 | 0.0610* | |
H13 | 0.27480 | 0.42330 | 0.18150 | 0.0610* | |
H14 | 0.11560 | 0.51450 | 0.11480 | 0.0490* | |
H15 | 0.14950 | 0.57950 | 0.04250 | 0.0490* | |
H16 | 0.43190 | 0.78360 | 0.27070 | 0.0580* | |
H17 | 0.47890 | 0.72090 | 0.37780 | 0.0580* | |
H18 | 0.33480 | 0.79860 | 0.42000 | 0.0590* | |
H19 | 0.38220 | 0.90560 | 0.37730 | 0.0590* | |
H20 | 0.23020 | 0.90950 | 0.23830 | 0.0490* | |
H21 | 0.17640 | 0.85960 | 0.30340 | 0.0490* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0335 (2) | 0.0386 (2) | 0.0257 (2) | −0.0010 (2) | 0.0173 (2) | 0.0001 (2) |
S1 | 0.0416 (4) | 0.0527 (5) | 0.0362 (4) | −0.0043 (3) | 0.0232 (3) | 0.0054 (3) |
N1 | 0.0375 (14) | 0.0471 (17) | 0.0312 (14) | 0.0010 (12) | 0.0177 (11) | 0.0025 (12) |
N2 | 0.057 (2) | 0.0517 (19) | 0.0315 (14) | 0.0037 (15) | 0.0162 (14) | 0.0037 (13) |
N3 | 0.0372 (14) | 0.0458 (16) | 0.0349 (14) | 0.0015 (12) | 0.0164 (12) | 0.0003 (13) |
N4 | 0.0485 (17) | 0.0501 (17) | 0.0316 (14) | −0.0057 (13) | 0.0246 (13) | −0.0012 (12) |
N5 | 0.0490 (17) | 0.0472 (17) | 0.0318 (14) | −0.0058 (13) | 0.0226 (13) | −0.0046 (12) |
N6 | 0.0473 (17) | 0.0433 (16) | 0.0369 (15) | −0.0022 (13) | 0.0211 (13) | −0.0040 (13) |
C1 | 0.0427 (18) | 0.0446 (19) | 0.0325 (16) | −0.0017 (15) | 0.0194 (14) | −0.0001 (14) |
C2 | 0.057 (2) | 0.058 (2) | 0.041 (2) | 0.012 (2) | 0.0096 (18) | −0.0013 (19) |
C3 | 0.037 (2) | 0.070 (3) | 0.058 (2) | 0.0057 (19) | 0.0121 (18) | −0.006 (2) |
C4 | 0.044 (2) | 0.063 (2) | 0.046 (2) | 0.0001 (18) | 0.0245 (17) | −0.0018 (19) |
C5 | 0.054 (2) | 0.046 (2) | 0.0344 (17) | 0.0047 (17) | 0.0156 (16) | 0.0055 (15) |
C6 | 0.059 (2) | 0.044 (2) | 0.0335 (16) | −0.0009 (17) | 0.0235 (16) | 0.0045 (14) |
C7 | 0.047 (2) | 0.066 (2) | 0.046 (2) | 0.0145 (19) | 0.0253 (17) | −0.0033 (19) |
C8 | 0.069 (2) | 0.049 (2) | 0.045 (2) | 0.0116 (19) | 0.031 (2) | −0.0071 (17) |
C9 | 0.0367 (18) | 0.058 (2) | 0.045 (2) | −0.0066 (17) | 0.0094 (15) | 0.0031 (19) |
C10 | 0.057 (2) | 0.043 (2) | 0.041 (2) | −0.0059 (17) | 0.0112 (17) | −0.0054 (16) |
P1 | 0.0437 (5) | 0.0468 (5) | 0.0452 (5) | 0.0057 (4) | 0.0196 (4) | 0.0026 (4) |
F1 | 0.084 (2) | 0.113 (3) | 0.102 (3) | 0.046 (2) | 0.012 (2) | 0.005 (2) |
F2 | 0.170 (5) | 0.072 (2) | 0.264 (7) | −0.021 (2) | 0.171 (5) | −0.006 (3) |
F3 | 0.103 (2) | 0.085 (2) | 0.073 (2) | 0.016 (2) | 0.0329 (19) | −0.0226 (18) |
F4 | 0.089 (2) | 0.148 (4) | 0.077 (2) | 0.048 (2) | −0.002 (2) | 0.002 (2) |
F5 | 0.182 (5) | 0.078 (2) | 0.265 (7) | 0.003 (3) | 0.180 (5) | 0.022 (3) |
F6 | 0.120 (3) | 0.112 (3) | 0.073 (2) | 0.015 (2) | 0.036 (2) | −0.027 (2) |
Cl1 | 0.0510 (5) | 0.0707 (7) | 0.0425 (5) | 0.0165 (4) | 0.0235 (4) | 0.0068 (4) |
Co1—S1 | 2.3187 (12) | N4—H9 | 0.9000 |
Co1—N1 | 1.930 (3) | N5—H15 | 0.9000 |
Co1—N3 | 1.944 (3) | N5—H14 | 0.9000 |
Co1—N4 | 1.954 (3) | N6—H21 | 0.9000 |
Co1—N5 | 1.966 (3) | N6—H20 | 0.9000 |
Co1—N6 | 1.970 (3) | C2—C3 | 1.389 (6) |
Co1—C1 | 2.566 (3) | C3—C4 | 1.378 (6) |
S1—C1 | 1.734 (4) | C5—C6 | 1.511 (5) |
P1—F3 | 1.592 (3) | C7—C8 | 1.504 (6) |
P1—F4 | 1.557 (5) | C9—C10 | 1.513 (6) |
P1—F5 | 1.551 (6) | C2—H1 | 0.9300 |
P1—F6 | 1.585 (4) | C3—H2 | 0.9300 |
P1—F1 | 1.595 (4) | C4—H3 | 0.9300 |
P1—F2 | 1.556 (6) | C5—H5 | 0.9700 |
N1—C1 | 1.354 (4) | C5—H4 | 0.9700 |
N1—C4 | 1.332 (5) | C6—H6 | 0.9700 |
N2—C2 | 1.333 (7) | C6—H7 | 0.9700 |
N2—C1 | 1.330 (4) | C7—H10 | 0.9700 |
N3—C5 | 1.506 (4) | C7—H11 | 0.9700 |
N3—C7 | 1.495 (5) | C8—H13 | 0.9700 |
N3—C9 | 1.491 (5) | C8—H12 | 0.9700 |
N4—C6 | 1.479 (5) | C9—H16 | 0.9700 |
N5—C8 | 1.498 (6) | C9—H17 | 0.9700 |
N6—C10 | 1.491 (5) | C10—H19 | 0.9700 |
N4—H8 | 0.9000 | C10—H18 | 0.9700 |
S1—Co1—N1 | 72.31 (9) | H14—N5—H15 | 108.00 |
S1—Co1—N3 | 101.96 (9) | Co1—N5—H14 | 109.00 |
S1—Co1—N4 | 170.71 (9) | H20—N6—H21 | 108.00 |
S1—Co1—N5 | 89.62 (9) | Co1—N6—H20 | 110.00 |
S1—Co1—N6 | 87.67 (9) | C10—N6—H21 | 110.00 |
S1—Co1—C1 | 41.18 (9) | Co1—N6—H21 | 110.00 |
N1—Co1—N3 | 173.92 (12) | C10—N6—H20 | 110.00 |
N1—Co1—N4 | 98.40 (12) | Co1—C1—N1 | 47.51 (15) |
N1—Co1—N5 | 91.63 (13) | Co1—C1—S1 | 61.73 (10) |
N1—Co1—N6 | 95.02 (13) | Co1—C1—N2 | 171.7 (3) |
N1—Co1—C1 | 31.15 (12) | N1—C1—N2 | 125.2 (4) |
N3—Co1—N4 | 87.33 (12) | S1—C1—N1 | 109.2 (2) |
N3—Co1—N5 | 86.23 (13) | S1—C1—N2 | 125.6 (3) |
N3—Co1—N6 | 86.65 (13) | N2—C2—C3 | 123.6 (4) |
N3—Co1—C1 | 143.02 (12) | C2—C3—C4 | 117.6 (4) |
N4—Co1—N5 | 90.85 (13) | N1—C4—C3 | 119.5 (4) |
N4—Co1—N6 | 93.09 (13) | N3—C5—C6 | 111.1 (2) |
N4—Co1—C1 | 129.54 (12) | N4—C6—C5 | 109.1 (3) |
N5—Co1—N6 | 171.69 (12) | N3—C7—C8 | 109.1 (3) |
N5—Co1—C1 | 89.96 (11) | N5—C8—C7 | 109.0 (3) |
N6—Co1—C1 | 93.16 (11) | N3—C9—C10 | 107.4 (3) |
Co1—S1—C1 | 77.09 (11) | N6—C10—C9 | 107.8 (3) |
F5—P1—F6 | 91.6 (3) | N2—C2—H1 | 118.00 |
F1—P1—F2 | 89.6 (3) | C3—C2—H1 | 118.00 |
F1—P1—F3 | 91.8 (2) | C2—C3—H2 | 121.00 |
F1—P1—F4 | 178.1 (2) | C4—C3—H2 | 121.00 |
F1—P1—F5 | 87.7 (3) | N1—C4—H3 | 120.00 |
F1—P1—F6 | 85.9 (2) | C3—C4—H3 | 120.00 |
F2—P1—F3 | 89.8 (3) | N3—C5—H5 | 109.00 |
F2—P1—F4 | 90.4 (3) | N3—C5—H4 | 109.00 |
F2—P1—F5 | 176.5 (4) | H4—C5—H5 | 108.00 |
F2—P1—F6 | 90.3 (3) | C6—C5—H4 | 109.00 |
F3—P1—F4 | 86.3 (2) | C6—C5—H5 | 109.00 |
F3—P1—F5 | 88.2 (3) | N4—C6—H6 | 110.00 |
F3—P1—F6 | 177.7 (2) | C5—C6—H7 | 110.00 |
F4—P1—F5 | 92.2 (3) | N4—C6—H7 | 110.00 |
F4—P1—F6 | 96.0 (2) | C5—C6—H6 | 110.00 |
Co1—N1—C1 | 101.4 (2) | H6—C6—H7 | 108.00 |
Co1—N1—C4 | 139.2 (3) | H10—C7—H11 | 108.00 |
C1—N1—C4 | 119.0 (3) | N3—C7—H10 | 110.00 |
C1—N2—C2 | 115.1 (3) | N3—C7—H11 | 110.00 |
Co1—N3—C5 | 110.3 (2) | C8—C7—H10 | 110.00 |
Co1—N3—C7 | 105.5 (2) | C8—C7—H11 | 110.00 |
Co1—N3—C9 | 106.6 (2) | N5—C8—H12 | 110.00 |
C5—N3—C7 | 112.3 (3) | N5—C8—H13 | 110.00 |
C5—N3—C9 | 109.3 (3) | C7—C8—H12 | 110.00 |
C7—N3—C9 | 112.6 (3) | C7—C8—H13 | 110.00 |
Co1—N4—C6 | 109.2 (2) | H12—C8—H13 | 108.00 |
Co1—N5—C8 | 110.8 (2) | N3—C9—H16 | 110.00 |
Co1—N6—C10 | 109.8 (2) | N3—C9—H17 | 110.00 |
C6—N4—H9 | 110.00 | C10—C9—H16 | 110.00 |
H8—N4—H9 | 108.00 | C10—C9—H17 | 110.00 |
Co1—N4—H8 | 110.00 | H16—C9—H17 | 108.00 |
C6—N4—H8 | 110.00 | N6—C10—H18 | 110.00 |
Co1—N4—H9 | 110.00 | N6—C10—H19 | 110.00 |
C8—N5—H14 | 110.00 | C9—C10—H18 | 110.00 |
C8—N5—H15 | 109.00 | C9—C10—H19 | 110.00 |
Co1—N5—H15 | 109.00 | H18—C10—H19 | 108.00 |
N1—Co1—S1—C1 | −1.46 (15) | N4—Co1—N6—C10 | 85.4 (2) |
N3—Co1—S1—C1 | 176.44 (15) | C1—Co1—N6—C10 | −144.7 (2) |
N5—Co1—S1—C1 | 90.38 (14) | S1—Co1—C1—N1 | −177.3 (3) |
N6—Co1—S1—C1 | −97.48 (14) | N1—Co1—C1—S1 | 177.3 (3) |
S1—Co1—N1—C1 | 1.86 (19) | N3—Co1—C1—S1 | −5.8 (2) |
S1—Co1—N1—C4 | 173.9 (4) | N3—Co1—C1—N1 | 176.9 (2) |
N4—Co1—N1—C1 | −178.3 (2) | N4—Co1—C1—S1 | 179.46 (13) |
N4—Co1—N1—C4 | −6.3 (4) | N4—Co1—C1—N1 | 2.2 (3) |
N5—Co1—N1—C1 | −87.2 (2) | N5—Co1—C1—S1 | −89.47 (12) |
N5—Co1—N1—C4 | 84.8 (4) | N5—Co1—C1—N1 | 93.2 (2) |
N6—Co1—N1—C1 | 87.8 (2) | N6—Co1—C1—S1 | 82.83 (12) |
N6—Co1—N1—C4 | −100.1 (4) | N6—Co1—C1—N1 | −94.5 (2) |
C1—Co1—N1—C4 | 172.1 (6) | Co1—S1—C1—N1 | 2.1 (2) |
S1—Co1—N3—C5 | −179.45 (19) | Co1—S1—C1—N2 | −175.4 (3) |
S1—Co1—N3—C7 | −58.0 (2) | Co1—N1—C1—S1 | −2.5 (3) |
S1—Co1—N3—C9 | 62.0 (2) | Co1—N1—C1—N2 | 175.0 (3) |
N4—Co1—N3—C5 | 0.4 (2) | C4—N1—C1—Co1 | −174.1 (4) |
N4—Co1—N3—C7 | 121.9 (3) | C4—N1—C1—S1 | −176.6 (3) |
N4—Co1—N3—C9 | −118.2 (2) | C4—N1—C1—N2 | 0.9 (6) |
N5—Co1—N3—C5 | −90.6 (2) | Co1—N1—C4—C3 | −170.8 (3) |
N5—Co1—N3—C7 | 30.8 (2) | C1—N1—C4—C3 | 0.3 (6) |
N5—Co1—N3—C9 | 150.8 (2) | C2—N2—C1—S1 | 175.8 (3) |
N6—Co1—N3—C5 | 93.6 (2) | C2—N2—C1—N1 | −1.2 (5) |
N6—Co1—N3—C7 | −144.9 (2) | C1—N2—C2—C3 | 0.4 (6) |
N6—Co1—N3—C9 | −24.9 (2) | Co1—N3—C5—C6 | 20.3 (3) |
C1—Co1—N3—C5 | −175.55 (18) | C7—N3—C5—C6 | −97.1 (3) |
C1—Co1—N3—C7 | −54.1 (3) | C9—N3—C5—C6 | 137.2 (3) |
C1—Co1—N3—C9 | 65.9 (3) | Co1—N3—C7—C8 | −47.1 (4) |
N1—Co1—N4—C6 | 156.7 (2) | C5—N3—C7—C8 | 73.1 (4) |
N3—Co1—N4—C6 | −21.3 (2) | C9—N3—C7—C8 | −163.0 (3) |
N5—Co1—N4—C6 | 64.9 (2) | Co1—N3—C9—C10 | 46.4 (3) |
N6—Co1—N4—C6 | −107.8 (2) | C5—N3—C9—C10 | −72.8 (4) |
C1—Co1—N4—C6 | 155.58 (18) | C7—N3—C9—C10 | 161.7 (3) |
S1—Co1—N5—C8 | 93.0 (2) | Co1—N4—C6—C5 | 37.0 (3) |
N1—Co1—N5—C8 | 165.3 (3) | Co1—N5—C8—C7 | −15.2 (4) |
N3—Co1—N5—C8 | −9.0 (3) | Co1—N6—C10—C9 | 27.8 (3) |
N4—Co1—N5—C8 | −96.3 (3) | N2—C2—C3—C4 | 0.6 (7) |
C1—Co1—N5—C8 | 134.2 (3) | C2—C3—C4—N1 | −1.0 (6) |
S1—Co1—N6—C10 | −103.9 (2) | N3—C5—C6—N4 | −37.6 (3) |
N1—Co1—N6—C10 | −175.9 (2) | N3—C7—C8—N5 | 40.9 (4) |
N3—Co1—N6—C10 | −1.8 (2) | N3—C9—C10—N6 | −48.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H8···N2i | 0.90 | 2.50 | 3.079 (4) | 123 |
N4—H9···Cl1ii | 0.90 | 2.52 | 3.278 (3) | 142 |
N5—H14···Cl1ii | 0.90 | 2.39 | 3.287 (3) | 173 |
N5—H15···Cl1iii | 0.90 | 2.42 | 3.273 (3) | 160 |
N6—H21···Cl1 | 0.90 | 2.29 | 3.187 (3) | 173 |
C6—H6···F1 | 0.97 | 2.39 | 3.210 (6) | 143 |
C7—H11···F4iv | 0.97 | 2.52 | 3.328 (6) | 141 |
C9—H17···F6v | 0.97 | 2.52 | 3.454 (6) | 161 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C4H3N2S)(C6H18N4)](Cl)PF6 |
Mr | 496.73 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 12.7106 (17), 11.326 (2), 14.205 (2) |
β (°) | 112.549 (10) |
V (Å3) | 1888.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.31 |
Crystal size (mm) | 0.45 × 0.35 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.503, 0.770 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 5201, 4342, 3416 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.174, 1.05 |
No. of reflections | 4342 |
No. of parameters | 237 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.14, −0.87 |
Computer programs: WinAFC (Rigaku/MSC, 2000), CrystalStructure (Rigaku/MSC, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H8···N2i | 0.90 | 2.50 | 3.079 (4) | 123 |
N4—H9···Cl1ii | 0.90 | 2.52 | 3.278 (3) | 142 |
N5—H14···Cl1ii | 0.90 | 2.39 | 3.287 (3) | 173 |
N5—H15···Cl1iii | 0.90 | 2.42 | 3.273 (3) | 160 |
N6—H21···Cl1 | 0.90 | 2.29 | 3.187 (3) | 173 |
C6—H6···F1 | 0.97 | 2.39 | 3.210 (6) | 143 |
C7—H11···F4iv | 0.97 | 2.52 | 3.328 (6) | 141 |
C9—H17···F6v | 0.97 | 2.52 | 3.454 (6) | 161 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2; (v) −x+1, −y+1, −z+1. |
Acknowledgements
This work was partially supported by Grants-in-Aid for Scientific Research C (No. 20550138) from the Japanese Society for the Promotion of Science (JSPS). The authors are grateful to Kochi University for financial support (The Kochi University President's Discretionary Grant 2009).
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.
Cobalt(III)-tren [tren = tris(2-aminoethyl)amine] complexes with thiolate and/or thioether ligands have been investigated in view of their stereochemistry and ligand substitution reactions (Mitsui & Kimura, et al., 1976; Jackson & Sargeson et al., 1978; Ohba & Saito, et al., 1984; Okamoto, et al., 1990; Kojima, et al., 1994; Yonemura, et al., 1997). The chemistry of the aliphatic and aromatic thiolato cobalt(III) complexes has led to many interesting results concerning the features of the coordinated sulfur atoms. Although aliphatic thiolato cobalt(III)-tren complexes have been extensively investigated, aromatic thiolato complexes have not been thus far because of the difficulties involved in their preparation.
In view of our interest in the stereochemistry and spectrochemical properties of aromatic and aliphatic cobalt(III) complexes, we synthesized the title compound using the tripod-like tetradentate tren ligand to fix the remaining two cis coordination sites in the cobalt(III) complexes, as two geometrical isomers, p-(trans(Nprim,S))and t-(trans(Ntert,S)), are possible for [Co(bidentate-N,S)(tren)]-type complexes. The known cobalt(III)-tren complexes of 2-aminoethanethiolate-N,S (aet) (Sargeson et al., 1978) formed p-isomers as the major products, and those of 2-mercaptoacetate-O,S (ma) or 3-mercaptopropionate-O,S (mp) selectively formed the t-isomers (Mitsui & Kimura, et al., 1976; Jackson & Sargeson et al., 1978; Ohba & Saito, et al., 1984; Okamoto, et al.,1990; Kojima, et al., 1994; Yonemura, et al., 1997). Herein we report on the structure of a cobalt(III)-tren complex coordinated with the aromatic thiolato ligand pyrimidine-2-thiolate (pymt).
In the title compound the cobalt(III) atom is coordinated by a tripod-like tetradentate ligand and a monoanionic N,S-bidentate ligand, producing an approximately octahedral CoN4OS geometry (Fig. 1). In the present complex the anionic sulfur atom of the pymt ligand is coordinated trans to the primary amine N-atom (Nprim) of the tren ligand, with a nearly linear S1—Co1—N4 angle (170.71 (9)Å) hence the title compound is the p-isomer (trans(Nprim,S)). The known cobalt(III)-tren complex of aet shows the same systematic trend, at least in the coordination manner of the N,S-bidentate ligand. The Co—S distance (2.3187 (12) Å) is significantly longer than those observed in the Co(III)-tren complexes with aliphatic thiolato ligands: 2.239 (1) Å in t-[Co{CH3SCH(CH3)COO}(tren)]2+ (Ohba & Saito, et al., 1984), 2.236 (2) Å in t-[Co(mp)(tren)]+ and 2.232 (1) Å in t-[Co(ma)(tren)]+ (Yonemura, et al., 1997)). The Co—N4 distance (1.954 (3) Å), which is in the trans position relative to the sulfur atom, is shorter than the other Co-N(tren) distances (Co1—N5 = 1.966 (3) Å and Co1—N6 = 1.970 (3) Å). The S1-Co1-N1 angle of 72.31 (9)° is far from the ideal angle of 90°. This distortion is relaxed by the other angles in the same plane, that is, S1-Co1-N3 = 101.96 (9), and N1-Co1-N4 = 98.40 (12)°. The other bond distances and angles are similar to those in the cobalt(III)-tren complexes mentioned above.
The aromatic pymt N,S-chelate ring is almost planar and the three N,N'-chelate rings of the tren are in a gauche conformation. The gauche conformations of the two –N—CH2—CH2—NH2 chelates in the tren ligand have unsymmetrical skew forms with the λ and δ conformations, and the gauche conformation of the central –N—CH2—CH2—NH2 chelate in the tren ligand has an unsymmetrical skew form with the λ conformation.
In the crystal structure each complex cation is linked to adjacent cations through N–H···N hydrogen bonds so constructing a one-dimensional chain structure (Fig. 2 and Table 1). These chains are further bridged by ordered Cl and PF6 anions through N–H···Cl and C–H···F contacts, leading to the formation of an infinite two-dimensional network (Table 1 and Fig. 2).