Bis(N,N-diethyl­dithio­carbamato)(1,10-phenanthroline)cobalt(III) tetra­fluorido­borate

Boyd, P.D.W.; Rickard, C.E.F.

doi:10.1107/S160053680801725X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m917-m918

doi:10.1107/S160053680801725X

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Bis(N,N-diethyldithiocarbamato)(1,10-phenanthroline)cobalt(III) tetrafluoridoborate

Peter D. W. Boyd ^a ^* and Clifton E. F. Rickard ^a

^aDepartment of Chemistry, The University of Auckland, Private Bag 92019, Auckland, New Zealand
^*Correspondence e-mail: pdw.boyd@auckland.ac.nz

(Received 15 April 2008; accepted 8 June 2008; online 13 June 2008)

The cationic complex in the structure of the title compound, [Co(Et₂NCS₂)₂(C₁₂H₈N₂)]BF₄, has a Co^III atom with a distorted octahedral coordination formed by four S atoms of two diethyldithiocarbamate and two N atoms of 1,10-phenanthroline ligands. The crystal structure features head-to-tail stacking of the phenanthroline ligands. The tetrafluoridoborate anions are positioned in the channels between the cation stacks running along the a axis, and form weak C—H⋯F interactions.

Related literature

For other bis(dialkyldithiocarbamato)L₂cobalt(III) complexes (L₂ = bismonodentate or bidentate ligands), see: Bhardwaj & Aftab (1990 ); Deplano & Trogu (1982 ); Deplano et al. (1983 ); Hendrickson et al. (1975 ); Holah & Murphy (1971 ); McCleverty et al. (1977 ); Okuno et al. (1989 ); Hodgson et al. (2008 ); Ware et al. (1998 ).

Experimental

Crystal data

[Co(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]BF₄
M_r = 622.46
Monoclinic, P 2₁ /n
a = 8.0064 (1) Å
b = 16.3421 (3) Å
c = 21.0927 (3) Å
β = 95.013 (1)°
V = 2749.24 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 203 (2) K
0.38 × 0.12 × 0.06 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.761, T_max = 0.944
16341 measured reflections
5982 independent reflections
4410 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.099
S = 1.07
5982 reflections
325 parameters
24 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co—S1	2.2805 (8)
Co—S2	2.2432 (8)
Co—S3	2.2590 (9)
Co—S4	2.2658 (8)
Co—N1	1.989 (2)
Co—N2	1.991 (2)

N1—Co—N2	82.86 (9)
N1—Co—S2	171.16 (7)
N2—Co—S2	94.35 (7)
N1—Co—S3	93.48 (7)
N2—Co—S3	165.93 (7)
S2—Co—S3	91.18 (3)
N1—Co—S4	93.98 (7)
N2—Co—S4	89.75 (7)
S2—Co—S4	94.39 (3)
S3—Co—S4	76.91 (3)
N1—Co—S1	95.48 (7)
N2—Co—S1	97.99 (7)
S2—Co—S1	76.56 (3)
S3—Co—S1	95.87 (3)
S4—Co—S1	168.45 (3)

Table 2
C-H⋯F contacts (Å, °)

D—H	A	D—H	H⋯A	D⋯A	D—H.·A
C10—H10A	F1ⁱ	0.94	2.31	3.169 (4)	151
C2—H2A	F2ⁱⁱ	0.94	2.43	3.281 (4)	151
C6—H6A	F4^iv	0.94	2.44	3.053 (4)	123
Symmetry codes (i) x, y, -1+z; (ii) $[-{\script{1\over 2}}+x, {\script{1\over 2}}-y, -{\script{1\over 2}}+z]$ ; (iii) 1-x, 1-y, 1-z; (iv) $[{\script{1\over 2}}-x, -{\script{1\over 2}}+y, {\script{1\over 2}}-z.]$

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680801725X/ya2076sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801725X/ya2076Isup2.hkl

checkCIF report

Comment top

The reaction of the bimetallic cobalt(III) complex [Co₂(Et₂NCS₂)₅]BF₄ (Hendrickson et al., 1975) with bidentate neutral and anionic ligands (L) has provided a convenient route for the preparation of mixed ligand cobalt(III) bisdithiocarbamate complexes such as [Co(Et₂NCS₂)₂L]BF₄ (McCleverty et al., 1977; Deplano & Trogu, 1982; Deplano et al., 1983; Ware et al., 1998; Hodgson et al., 2008). Several papers on the preparation of diimine complexes with L=2,2'-bipyridine or 1,10-phenantholine have been published (Holah & Murphy, 1971; Okuno et al., 1989; Bhardwaj & Aftab, 1990; Hodgson et al., 2008). In the present communication the crystal structure of [Co(Et₂NCS₂)₂L]BF₄ (L=1,10-phenanthroline)(I), formed by reaction of [Co₂((C₂H₅)₂NCS₂)₅]BF₄ with 1,10-phenanthroline, is reported.

The molecular structure of (I) is shown in Fig. 1. The Co atom has a distorted octahedral coordination formed by four S atoms of two dithiocarbamate and two N atoms of 1,10-phenanthroline ligands (Table 1).

The crystal packing of the title compound (Fig. 2) features head-to-tail cationic complexes assembled in the crystal via stacking of the phenanthroline ligands in an alternating mode (interplanar distance is 3.57 Å). The tetrafluoroborate anions are located in the channels between the cation stacks running along the a axis of the structure and are held in position by many C—H···F interactions between phenanthroline C—H bonds and the F atoms of the tetrafluoroborate anion, (Table 2).

Related literature top

For other bis(dialkyldithiocarbamato)L₂cobalt(III) complexes (L₂= bismonodentate or bidentate ligands), see: Bhardwaj & Aftab (1990); Deplano & Trogu (1982); Deplano et al. (1983); Hendrickson et al. (1975); Holah & Murphy (1971); McCleverty et al. (1977); Okuno et al. (1989); Hodgson et al. (2008); Ware et al. (1998).

Experimental top

The complex(I) was prepared by reaction of equimolar amounts of [Co₂((C₂H₅)₂NCS₂)₅]BF₄ (Hendrickson et al., 1975) and 1,10-phenanthroline in dichloromethane solution at room temperature following the same procedure to that reported for the synthesis of the analogous dimethyldithiocarbamate complex (Hodgson et al., 2008). Crystals were grown from a dichloromethane solution.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Structure of (I) showing 50% probability displacement ellipsoids; the H atoms are omitted for clarity.
	Fig. 2. The crystal packing of the title compound viewed along the a axis showing stacking of phenanthroline ligands as well as the channels between cation stacks occupied by the BF₄^- ions.

Bis(N,N-diethyldithiocarbamato)(1,10-phenanthroline)cobalt(III) tetrafluoridoborate top

Crystal data top

[Co(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]BF₄	F(000) = 1280
M_r = 622.46	D_x = 1.504 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.0064 (1) Å	Cell parameters from 8163 reflections
b = 16.3421 (3) Å	θ = 1.9–27.5°
c = 21.0927 (3) Å	µ = 0.97 mm⁻¹
β = 95.013 (1)°	T = 203 K
V = 2749.24 (7) Å³	Needle, red
Z = 4	0.38 × 0.12 × 0.06 mm

Data collection top

Siemens SMART CCD diffractometer	5982 independent reflections
Radiation source: fine-focus sealed tube	4410 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.761, T_max = 0.944	k = −19→20
16341 measured reflections	l = −17→27

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.023P)² + 3.5289P] where P = (F_o² + 2F_c²)/3
5982 reflections	(Δ/σ)_max < 0.001
325 parameters	Δρ_max = 0.49 e Å⁻³
24 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Co(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]BF₄	V = 2749.24 (7) Å³
M_r = 622.46	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.0064 (1) Å	µ = 0.97 mm⁻¹
b = 16.3421 (3) Å	T = 203 K
c = 21.0927 (3) Å	0.38 × 0.12 × 0.06 mm
β = 95.013 (1)°

Data collection top

Siemens SMART CCD diffractometer	5982 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4410 reflections with I > 2σ(I)
T_min = 0.761, T_max = 0.944	R_int = 0.025
16341 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	24 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.07	Δρ_max = 0.49 e Å⁻³
5982 reflections	Δρ_min = −0.44 e Å⁻³
325 parameters

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

	x	y	z	U_iso*/U_eq
Co	0.18850 (5)	0.24157 (2)	0.017869 (19)	0.02837 (11)
S1	−0.08717 (9)	0.25666 (4)	−0.01750 (4)	0.03400 (18)
S2	0.18002 (9)	0.36489 (4)	−0.02902 (4)	0.03424 (18)
S3	0.16723 (10)	0.29916 (5)	0.11419 (4)	0.03561 (19)
S4	0.45935 (9)	0.25371 (5)	0.05787 (4)	0.03378 (18)
N1	0.1650 (3)	0.12827 (14)	0.05041 (11)	0.0287 (5)
N2	0.2630 (3)	0.18340 (14)	−0.05766 (11)	0.0296 (5)
N3	−0.1280 (3)	0.39591 (15)	−0.08739 (13)	0.0369 (6)
N4	0.4748 (3)	0.31052 (16)	0.17814 (13)	0.0405 (6)
C1	0.1077 (4)	0.10206 (19)	0.10422 (15)	0.0360 (7)
H1A	0.0660	0.1406	0.1319	0.043*
C2	0.1072 (4)	0.01878 (19)	0.12111 (16)	0.0405 (8)
H2A	0.0649	0.0024	0.1593	0.049*
C3	0.1684 (4)	−0.03832 (18)	0.08182 (16)	0.0372 (7)
H3A	0.1702	−0.0939	0.0932	0.045*
C4	0.2289 (4)	−0.01328 (17)	0.02424 (15)	0.0310 (6)
C5	0.2980 (4)	−0.06714 (17)	−0.02050 (16)	0.0359 (7)
H5A	0.3055	−0.1234	−0.0115	0.043*
C6	0.3526 (4)	−0.03887 (18)	−0.07522 (16)	0.0373 (7)
H6A	0.3979	−0.0758	−0.1033	0.045*
C7	0.3427 (4)	0.04682 (18)	−0.09137 (14)	0.0319 (7)
C8	0.3982 (4)	0.0808 (2)	−0.14704 (15)	0.0397 (8)
H8A	0.4425	0.0472	−0.1776	0.048*
C9	0.3868 (4)	0.1636 (2)	−0.15598 (15)	0.0410 (8)
H9A	0.4256	0.1872	−0.1926	0.049*
C10	0.3178 (4)	0.21330 (19)	−0.11098 (15)	0.0368 (7)
H10A	0.3097	0.2699	−0.1186	0.044*
C11	0.2767 (3)	0.10037 (16)	−0.04794 (14)	0.0277 (6)
C12	0.2215 (3)	0.07098 (16)	0.01001 (13)	0.0273 (6)
C21	−0.0290 (4)	0.34776 (17)	−0.05069 (15)	0.0312 (7)
C22	−0.3106 (4)	0.38155 (19)	−0.09710 (17)	0.0419 (8)
H22A	−0.3370	0.3281	−0.0793	0.050*
H22B	−0.3455	0.3806	−0.1428	0.050*
C23	−0.4057 (5)	0.4470 (3)	−0.0658 (3)	0.0801 (15)
H23A	−0.5250	0.4362	−0.0729	0.120*
H23B	−0.3810	0.4998	−0.0839	0.120*
H23C	−0.3726	0.4474	−0.0205	0.120*
C24	−0.0615 (4)	0.46964 (19)	−0.11725 (17)	0.0438 (8)
H24A	0.0600	0.4722	−0.1068	0.053*
H24B	−0.1111	0.5184	−0.0994	0.053*
C25	−0.0982 (5)	0.4703 (2)	−0.18846 (19)	0.0620 (11)
H25A	−0.0524	0.5197	−0.2057	0.093*
H25B	−0.2185	0.4689	−0.1991	0.093*
H25C	−0.0472	0.4228	−0.2065	0.093*
C31	0.3820 (4)	0.29130 (17)	0.12572 (15)	0.0329 (7)
C32	0.4009 (5)	0.3398 (2)	0.23524 (16)	0.0501 (9)
H32A	0.2940	0.3670	0.2226	0.060*
H32B	0.4759	0.3803	0.2570	0.060*
C33	0.3713 (6)	0.2702 (3)	0.2810 (2)	0.0727 (13)
H33A	0.3222	0.2919	0.3180	0.109*
H33B	0.4772	0.2440	0.2944	0.109*
H33C	0.2956	0.2305	0.2599	0.109*
C34	0.6587 (4)	0.3015 (2)	0.18175 (19)	0.0574 (10)
H34A	0.6872	0.2552	0.1552	0.069*
H34B	0.7009	0.2894	0.2258	0.069*
C35	0.7437 (5)	0.3778 (3)	0.1599 (3)	0.0833 (16)
H35A	0.8640	0.3694	0.1630	0.125*
H35B	0.7176	0.4236	0.1866	0.125*
H35C	0.7039	0.3894	0.1160	0.125*
B	0.8580 (6)	0.1060 (2)	0.25563 (19)	0.0456 (10)
F1	0.7989 (3)	0.11912 (17)	0.31314 (12)	0.0873 (8)
F2	0.9614 (4)	0.16960 (17)	0.24311 (15)	0.0952 (9)
F3	0.9452 (5)	0.03466 (17)	0.25818 (16)	0.1194 (13)
F4	0.7309 (5)	0.1022 (2)	0.21044 (15)	0.1376 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0281 (2)	0.02278 (19)	0.0343 (2)	0.00121 (16)	0.00333 (16)	0.00146 (17)
S1	0.0298 (4)	0.0249 (4)	0.0470 (5)	−0.0036 (3)	0.0017 (3)	0.0067 (3)
S2	0.0272 (4)	0.0250 (4)	0.0502 (5)	−0.0023 (3)	0.0017 (3)	0.0057 (3)
S3	0.0340 (4)	0.0307 (4)	0.0428 (5)	0.0030 (3)	0.0074 (3)	−0.0053 (3)
S4	0.0285 (4)	0.0332 (4)	0.0396 (4)	0.0043 (3)	0.0032 (3)	−0.0035 (3)
N1	0.0299 (13)	0.0264 (12)	0.0297 (13)	−0.0001 (10)	0.0025 (10)	0.0002 (10)
N2	0.0306 (13)	0.0284 (13)	0.0294 (13)	0.0003 (10)	0.0001 (10)	0.0027 (10)
N3	0.0284 (13)	0.0289 (13)	0.0526 (17)	−0.0021 (10)	−0.0012 (12)	0.0097 (12)
N4	0.0423 (16)	0.0350 (14)	0.0433 (16)	0.0025 (12)	−0.0014 (13)	−0.0070 (12)
C1	0.0387 (17)	0.0347 (16)	0.0355 (17)	0.0014 (13)	0.0086 (14)	0.0015 (14)
C2	0.0456 (19)	0.0361 (17)	0.0407 (19)	−0.0025 (14)	0.0093 (15)	0.0087 (15)
C3	0.0386 (18)	0.0262 (15)	0.0469 (19)	−0.0030 (13)	0.0045 (15)	0.0074 (14)
C4	0.0278 (15)	0.0261 (14)	0.0384 (17)	−0.0004 (11)	−0.0014 (13)	−0.0004 (13)
C5	0.0340 (17)	0.0218 (14)	0.052 (2)	−0.0013 (12)	0.0013 (14)	−0.0027 (14)
C6	0.0373 (17)	0.0304 (16)	0.0441 (19)	0.0002 (13)	0.0030 (14)	−0.0093 (14)
C7	0.0290 (16)	0.0328 (15)	0.0333 (17)	−0.0006 (12)	−0.0001 (13)	−0.0030 (13)
C8	0.0390 (18)	0.0471 (19)	0.0328 (18)	0.0015 (15)	0.0021 (14)	−0.0047 (15)
C9	0.0430 (19)	0.053 (2)	0.0271 (16)	−0.0004 (15)	0.0023 (14)	0.0070 (15)
C10	0.0385 (18)	0.0377 (17)	0.0339 (17)	0.0004 (14)	0.0006 (14)	0.0069 (14)
C11	0.0252 (14)	0.0246 (14)	0.0324 (16)	0.0008 (11)	−0.0024 (12)	−0.0036 (12)
C12	0.0258 (14)	0.0265 (14)	0.0293 (16)	0.0000 (11)	0.0002 (12)	−0.0003 (12)
C21	0.0307 (16)	0.0233 (14)	0.0397 (17)	−0.0003 (11)	0.0039 (13)	−0.0019 (13)
C22	0.0291 (16)	0.0364 (17)	0.059 (2)	−0.0033 (13)	−0.0038 (15)	0.0119 (16)
C23	0.036 (2)	0.089 (3)	0.118 (4)	−0.004 (2)	0.018 (2)	−0.035 (3)
C24	0.0381 (18)	0.0285 (16)	0.064 (2)	−0.0036 (13)	0.0017 (16)	0.0164 (16)
C25	0.074 (3)	0.052 (2)	0.062 (3)	−0.007 (2)	0.015 (2)	0.013 (2)
C31	0.0360 (17)	0.0242 (14)	0.0381 (17)	0.0012 (12)	0.0016 (14)	0.0002 (13)
C32	0.065 (2)	0.045 (2)	0.040 (2)	−0.0035 (17)	0.0006 (17)	−0.0140 (16)
C33	0.098 (4)	0.071 (3)	0.049 (2)	−0.013 (3)	0.009 (2)	−0.002 (2)
C34	0.045 (2)	0.063 (2)	0.060 (2)	0.0132 (18)	−0.0192 (18)	−0.022 (2)
C35	0.043 (2)	0.075 (3)	0.134 (5)	−0.010 (2)	0.018 (3)	−0.037 (3)
B	0.058 (3)	0.041 (2)	0.037 (2)	0.0036 (19)	0.0057 (19)	−0.0055 (18)
F1	0.100 (2)	0.102 (2)	0.0643 (16)	−0.0059 (16)	0.0286 (15)	−0.0340 (15)
F2	0.091 (2)	0.0754 (18)	0.123 (2)	−0.0163 (15)	0.0321 (18)	0.0104 (17)
F3	0.179 (3)	0.0618 (17)	0.129 (3)	0.0507 (19)	0.080 (3)	0.0205 (17)
F4	0.178 (3)	0.130 (3)	0.090 (2)	−0.036 (3)	−0.070 (2)	−0.003 (2)

Geometric parameters (Å, º) top

Co—S1	2.2805 (8)	C8—C9	1.367 (5)
Co—S2	2.2432 (8)	C8—H8A	0.9400
Co—S3	2.2590 (9)	C9—C10	1.400 (4)
Co—S4	2.2658 (8)	C9—H9A	0.9400
Co—N1	1.989 (2)	C10—H10A	0.9400
Co—N2	1.991 (2)	C11—C12	1.419 (4)
S1—C21	1.726 (3)	C22—C23	1.499 (5)
S2—C21	1.719 (3)	C22—H22A	0.9800
S3—C31	1.720 (3)	C22—H22B	0.9800
S4—C31	1.722 (3)	C23—H23A	0.9700
N1—C1	1.332 (4)	C23—H23B	0.9700
N1—C12	1.369 (3)	C23—H23C	0.9700
N2—C10	1.335 (4)	C24—C25	1.505 (5)
N2—C11	1.375 (3)	C24—H24A	0.9800
N3—C21	1.319 (4)	C24—H24B	0.9800
N3—C22	1.477 (4)	C25—H25A	0.9700
N3—C24	1.480 (4)	C25—H25B	0.9700
N4—C31	1.315 (4)	C25—H25C	0.9700
N4—C32	1.468 (4)	C32—C33	1.524 (5)
N4—C34	1.475 (4)	C32—H32A	0.9800
C1—C2	1.407 (4)	C32—H32B	0.9800
C1—H1A	0.9400	C33—H33A	0.9700
C2—C3	1.367 (4)	C33—H33B	0.9700
C2—H2A	0.9400	C33—H33C	0.9700
C3—C4	1.407 (4)	C34—C35	1.512 (6)
C3—H3A	0.9400	C34—H34A	0.9800
C4—C12	1.409 (4)	C34—H34B	0.9800
C4—C5	1.437 (4)	C35—H35A	0.9700
C5—C6	1.351 (4)	C35—H35B	0.9700
C5—H5A	0.9400	C35—H35C	0.9700
C6—C7	1.442 (4)	B—F4	1.333 (5)
C6—H6A	0.9400	B—F3	1.357 (5)
C7—C11	1.403 (4)	B—F1	1.357 (5)
C7—C8	1.406 (4)	B—F2	1.369 (5)

N1—Co—N2	82.86 (9)	N1—C12—C4	123.1 (3)
N1—Co—S2	171.16 (7)	N1—C12—C11	116.7 (2)
N2—Co—S2	94.35 (7)	C4—C12—C11	120.2 (3)
N1—Co—S3	93.48 (7)	N3—C21—S2	125.5 (2)
N2—Co—S3	165.93 (7)	N3—C21—S1	125.6 (2)
S2—Co—S3	91.18 (3)	S2—C21—S1	108.88 (16)
N1—Co—S4	93.98 (7)	N3—C22—C23	111.1 (3)
N2—Co—S4	89.75 (7)	N3—C22—H22A	109.4
S2—Co—S4	94.39 (3)	C23—C22—H22A	109.4
S3—Co—S4	76.91 (3)	N3—C22—H22B	109.4
N1—Co—S1	95.48 (7)	C23—C22—H22B	109.4
N2—Co—S1	97.99 (7)	H22A—C22—H22B	108.0
S2—Co—S1	76.56 (3)	C22—C23—H23A	109.5
S3—Co—S1	95.87 (3)	C22—C23—H23B	109.5
S4—Co—S1	168.45 (3)	H23A—C23—H23B	109.5
C21—S1—Co	86.45 (10)	C22—C23—H23C	109.5
C21—S2—Co	87.84 (10)	H23A—C23—H23C	109.5
C31—S3—Co	86.73 (11)	H23B—C23—H23C	109.5
C31—S4—Co	86.48 (10)	N3—C24—C25	112.6 (3)
C1—N1—C12	117.9 (2)	N3—C24—H24A	109.1
C1—N1—Co	130.1 (2)	C25—C24—H24A	109.1
C12—N1—Co	112.05 (18)	N3—C24—H24B	109.1
C10—N2—C11	117.3 (3)	C25—C24—H24B	109.1
C10—N2—Co	130.0 (2)	H24A—C24—H24B	107.8
C11—N2—Co	112.17 (19)	C24—C25—H25A	109.5
C21—N3—C22	121.6 (2)	C24—C25—H25B	109.5
C21—N3—C24	121.0 (2)	H25A—C25—H25B	109.5
C22—N3—C24	117.3 (2)	C24—C25—H25C	109.5
C31—N4—C32	121.9 (3)	H25A—C25—H25C	109.5
C31—N4—C34	120.5 (3)	H25B—C25—H25C	109.5
C32—N4—C34	117.6 (3)	N4—C31—S3	125.8 (2)
N1—C1—C2	122.4 (3)	N4—C31—S4	124.5 (2)
N1—C1—H1A	118.8	S3—C31—S4	109.69 (17)
C2—C1—H1A	118.8	N4—C32—C33	111.9 (3)
C3—C2—C1	119.9 (3)	N4—C32—H32A	109.2
C3—C2—H2A	120.1	C33—C32—H32A	109.2
C1—C2—H2A	120.1	N4—C32—H32B	109.2
C2—C3—C4	119.6 (3)	C33—C32—H32B	109.2
C2—C3—H3A	120.2	H32A—C32—H32B	107.9
C4—C3—H3A	120.2	C32—C33—H33A	109.5
C3—C4—C12	117.2 (3)	C32—C33—H33B	109.5
C3—C4—C5	124.8 (3)	H33A—C33—H33B	109.5
C12—C4—C5	118.1 (3)	C32—C33—H33C	109.5
C6—C5—C4	121.6 (3)	H33A—C33—H33C	109.5
C6—C5—H5A	119.2	H33B—C33—H33C	109.5
C4—C5—H5A	119.2	N4—C34—C35	112.0 (3)
C5—C6—C7	121.3 (3)	N4—C34—H34A	109.2
C5—C6—H6A	119.4	C35—C34—H34A	109.2
C7—C6—H6A	119.4	N4—C34—H34B	109.2
C11—C7—C8	117.6 (3)	C35—C34—H34B	109.2
C11—C7—C6	117.9 (3)	H34A—C34—H34B	107.9
C8—C7—C6	124.5 (3)	C34—C35—H35A	109.5
C9—C8—C7	118.9 (3)	C34—C35—H35B	109.5
C9—C8—H8A	120.5	H35A—C35—H35B	109.5
C7—C8—H8A	120.5	C34—C35—H35C	109.5
C8—C9—C10	120.4 (3)	H35A—C35—H35C	109.5
C8—C9—H9A	119.8	H35B—C35—H35C	109.5
C10—C9—H9A	119.8	F4—B—F3	110.3 (4)
N2—C10—C9	122.5 (3)	F4—B—F1	110.0 (4)
N2—C10—H10A	118.8	F3—B—F1	108.6 (3)
C9—C10—H10A	118.8	F4—B—F2	109.5 (4)
N2—C11—C7	123.2 (3)	F3—B—F2	110.0 (4)
N2—C11—C12	115.8 (2)	F1—B—F2	108.4 (3)
C7—C11—C12	121.0 (3)

N1—Co—S1—C21	−172.69 (12)	C6—C7—C8—C9	−177.9 (3)
N2—Co—S1—C21	−89.16 (12)	C7—C8—C9—C10	−1.3 (5)
S2—Co—S1—C21	3.43 (10)	C11—N2—C10—C9	0.0 (4)
S3—Co—S1—C21	93.23 (10)	Co—N2—C10—C9	171.2 (2)
S4—Co—S1—C21	42.5 (2)	C8—C9—C10—N2	1.0 (5)
N2—Co—S2—C21	93.75 (12)	C10—N2—C11—C7	−0.8 (4)
S3—Co—S2—C21	−99.20 (10)	Co—N2—C11—C7	−173.5 (2)
S4—Co—S2—C21	−176.16 (10)	C10—N2—C11—C12	178.4 (2)
S1—Co—S2—C21	−3.44 (10)	Co—N2—C11—C12	5.7 (3)
N1—Co—S3—C31	90.50 (12)	C8—C7—C11—N2	0.6 (4)
N2—Co—S3—C31	16.2 (3)	C6—C7—C11—N2	179.1 (3)
S2—Co—S3—C31	−97.02 (10)	C8—C7—C11—C12	−178.6 (3)
S4—Co—S3—C31	−2.78 (10)	C6—C7—C11—C12	0.0 (4)
S1—Co—S3—C31	−173.62 (10)	C1—N1—C12—C4	−3.1 (4)
N1—Co—S4—C31	−89.87 (12)	Co—N1—C12—C4	175.6 (2)
N2—Co—S4—C31	−172.70 (12)	C1—N1—C12—C11	178.0 (3)
S2—Co—S4—C31	92.96 (10)	Co—N1—C12—C11	−3.3 (3)
S3—Co—S4—C31	2.78 (10)	C3—C4—C12—N1	2.5 (4)
S1—Co—S4—C31	55.0 (2)	C5—C4—C12—N1	−177.0 (3)
N2—Co—N1—C1	−176.5 (3)	C3—C4—C12—C11	−178.6 (3)
S3—Co—N1—C1	17.1 (3)	C5—C4—C12—C11	1.8 (4)
S4—Co—N1—C1	94.2 (3)	N2—C11—C12—N1	−1.6 (4)
S1—Co—N1—C1	−79.1 (3)	C7—C11—C12—N1	177.6 (2)
N2—Co—N1—C12	4.96 (19)	N2—C11—C12—C4	179.4 (3)
S3—Co—N1—C12	−161.39 (18)	C7—C11—C12—C4	−1.4 (4)
S4—Co—N1—C12	−84.29 (18)	C22—N3—C21—S2	−172.4 (2)
S1—Co—N1—C12	102.36 (18)	C24—N3—C21—S2	3.7 (4)
N1—Co—N2—C10	−177.3 (3)	C22—N3—C21—S1	8.5 (4)
S2—Co—N2—C10	11.1 (3)	C24—N3—C21—S1	−175.3 (2)
S3—Co—N2—C10	−101.7 (4)	Co—S2—C21—N3	−174.5 (3)
S4—Co—N2—C10	−83.3 (3)	Co—S2—C21—S1	4.67 (14)
S1—Co—N2—C10	88.1 (3)	Co—S1—C21—N3	174.6 (3)
N1—Co—N2—C11	−5.82 (19)	Co—S1—C21—S2	−4.60 (14)
S2—Co—N2—C11	−177.39 (18)	C21—N3—C22—C23	110.7 (4)
S3—Co—N2—C11	69.8 (4)	C24—N3—C22—C23	−65.5 (4)
S4—Co—N2—C11	88.22 (18)	C21—N3—C24—C25	124.4 (3)
S1—Co—N2—C11	−100.38 (18)	C22—N3—C24—C25	−59.4 (4)
C12—N1—C1—C2	1.5 (4)	C32—N4—C31—S3	1.8 (4)
Co—N1—C1—C2	−176.9 (2)	C34—N4—C31—S3	−179.5 (3)
N1—C1—C2—C3	0.5 (5)	C32—N4—C31—S4	−178.0 (2)
C1—C2—C3—C4	−1.1 (5)	C34—N4—C31—S4	0.7 (4)
C2—C3—C4—C12	−0.4 (4)	Co—S3—C31—N4	−176.0 (3)
C2—C3—C4—C5	179.2 (3)	Co—S3—C31—S4	3.78 (13)
C3—C4—C5—C6	179.5 (3)	Co—S4—C31—N4	176.0 (3)
C12—C4—C5—C6	−1.0 (4)	Co—S4—C31—S3	−3.77 (13)
C4—C5—C6—C7	−0.4 (5)	C31—N4—C32—C33	93.6 (4)
C5—C6—C7—C11	0.9 (4)	C34—N4—C32—C33	−85.1 (4)
C5—C6—C7—C8	179.4 (3)	C31—N4—C34—C35	89.0 (4)
C11—C7—C8—C9	0.5 (4)	C32—N4—C34—C35	−92.2 (4)

Experimental details

Crystal data
Chemical formula	[Co(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]BF₄
M_r	622.46
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	203
a, b, c (Å)	8.0064 (1), 16.3421 (3), 21.0927 (3)
β (°)	95.013 (1)
V (Å³)	2749.24 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.38 × 0.12 × 0.06

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.761, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	16341, 5982, 4410
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.099, 1.07
No. of reflections	5982
No. of parameters	325
No. of restraints	24
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.44

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Co—S1	2.2805 (8)	Co—S4	2.2658 (8)
Co—S2	2.2432 (8)	Co—N1	1.989 (2)
Co—S3	2.2590 (9)	Co—N2	1.991 (2)

N1—Co—N2	82.86 (9)	S2—Co—S4	94.39 (3)
N1—Co—S2	171.16 (7)	S3—Co—S4	76.91 (3)
N2—Co—S2	94.35 (7)	N1—Co—S1	95.48 (7)
N1—Co—S3	93.48 (7)	N2—Co—S1	97.99 (7)
N2—Co—S3	165.93 (7)	S2—Co—S1	76.56 (3)
S2—Co—S3	91.18 (3)	S3—Co—S1	95.87 (3)
N1—Co—S4	93.98 (7)	S4—Co—S1	168.45 (3)
N2—Co—S4	89.75 (7)

C-H···F contacts in (I) (Å, deg) top

D-H	A	D-H	H···A	D···A	D-H..A
C10-H10A	F1ⁱ	0.94	2.31	3.169 (4)	151.2
C2-H2A	F2ⁱⁱ	0.94	2.43	3.281 (4)	150.9
C6-H6A	F4^iv	0.94	2.44	3.053 (4)	122.9

Symmetry codes (i) x,y,-1+z (ii) -1/2+x,1/2-y,-1/2+z (iii) 1-x,1-y,1-z (iv) 1/2-x,-1/2+y,1/2-z

Acknowledgements

This work was supported by the University of Auckland Research Committee. We thank Janet Hope for her assistance in the preparation of the complex.

References

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