trans-(Pyrimidine-2-thiol­ato-κ2N,S)[tris­(2-amino­ethyl)amine-κ4N,N′,N′′,N′′′]cobalt(III) chloride hexa­fluoridophosphate

Fujihara, K.; Yonemura, T.

doi:10.1107/S1600536809032395

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Pages m1127-m1128

doi:10.1107/S1600536809032395

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trans-(Pyrimidine-2-thiolato-κ²N,S)[tris(2-aminoethyl)amine-κ⁴N,N′,N′′,N′′′]cobalt(III) chloride hexafluoridophosphate

Keisuke Fujihara ^a and Toshiaki Yonemura ^a ^*

^aDepartment of Applied Science, Faculty of Science, Kochi University, Akebono-cho, Kochi 780-8520, Japan
^*Correspondence e-mail: yonemura@kochi-u.ac.jp

(Received 15 August 2009; accepted 15 August 2009; online 22 August 2009)

In the title compound, [Co(C₄H₃N₂S)(C₆H₁₈N₄)](Cl)PF₆, the Co^III 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 crystal structure 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

[Co(C₄H₃N₂S)(C₆H₁₈N₄)](Cl)PF₆
M_r = 496.73
Monoclinic, P 2₁ /c
a = 12.7106 (17) Å
b = 11.326 (2) Å
c = 14.205 (2) Å
β = 112.549 (10)°
V = 1888.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 296 K
0.45 × 0.35 × 0.20 mm

Data collection

Rigaku AFC-7S diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.503, T_max = 0.770
5201 measured reflections
4342 independent reflections
3416 reflections with F² > 2σ(F²)
R_int = 0.031
3 standard reflections every 150 reflections intensity decay: 5.4%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.174
S = 1.05
4342 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯F4^iv	0.97	2.52	3.328 (6)	141
C9—H17⋯F6^v	0.97	2.52	3.454 (6)	161
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z+1.

Data collection: WinAFC (Rigaku/MSC, 2000 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032395/su2138sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032395/su2138Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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%.

Computing details top

Data collection: WinAFC (Rigaku/MSC, 2000); cell refinement: 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).

Figures top

	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).

trans-(Pyrimidine-2-thiolato-κ²N,S)[tris(2- aminoethyl)amine-κ⁴N,N',N'',N''']cobalt(III) chloride hexafluoridophosphate top

Crystal data top

[Co(C₄H₃N₂S)(C₆H₁₈N₄)](Cl)PF₆	F(000) = 1008.0
M_r = 496.73	D_x = 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

Data collection top

Rigaku AFC-7S diffractometer	R_int = 0.031
ω–2θ scans	θ_max = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −16→15
T_min = 0.503, T_max = 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 top

Refinement on F²	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.057	w = 1/[σ²(F_o²) + (0.1106P)² + 1.816P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.174	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 1.14 e Å⁻³
4342 reflections	Δρ_min = −0.87 e Å⁻³
237 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.0077 (13)

Crystal data top

[Co(C₄H₃N₂S)(C₆H₁₈N₄)](Cl)PF₆	V = 1888.7 (5) Å³
M_r = 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)°

Data collection top

Rigaku AFC-7S diffractometer	3416 reflections with F² > 2σ(F²)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.031
T_min = 0.503, T_max = 0.770	3 standard reflections every 150 reflections
5201 measured reflections	intensity decay: 5.4%
4342 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.174	H-atom parameters constrained
S = 1.05	Δρ_max = 1.14 e Å⁻³
4342 reflections	Δρ_min = −0.87 e Å⁻³
237 parameters

Special details top

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···F4^iv	0.97	2.52	3.328 (6)	141
C9—H17···F6^v	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
M_r	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)
T_min, T_max	0.503, 0.770
No. of measured, independent and observed [F² > 2σ(F²)] reflections	5201, 4342, 3416
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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···F4^iv	0.97	2.52	3.328 (6)	141
C9—H17···F6^v	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).

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