Bis(μ-N,N-dimethyldithiocarbamato-κ³S,S′:S′)bis[(dimethoxyphenylphosphane-κP)(N,N-dimethyldithiocarbamato-κ²S,S′)cobalt(III)] bis(hexafluorophosphate)

Purple prismatic crystals of the title compound, [Co₂(C₃H₆NS₂)₄(C₈H₁₁O₂P)₂](PF₆)₂, were obtained by repeated recrystallization of trans-[Co(C₃H₆NS₂)₂-(C₈H₁₁O₂P)₂]PF₆ from CH₃CN/Et₂O and then from MeOH/CH₂Cl₂; during recrystallization one of the P(OMe)₂Ph ligands was dissociated from the Co^III center and the resulting Co^III complex fragment underwent dimerization. The complex cation has a dinuclear structure bridged by one S atom of each of two of the N,N-di­methyl­di­thio­carbamate ligands, and has crystallographically imposed C₂ symmetry. Two P(OMe)₂Ph ligands are coordinated at the transoid positions of the Co₂(μ-C₃H₆NS₂)₂(C₃H₆NS₂)₂ moiety, with Co—P bond lengths of 2.1921 (11) Å.

S1. Comment

We have undertaken the systematic syntheses and comparison of the structures, chemical and spectroscopic properties of several series of cobalt(III) complexes containing monodentate P-donor ligands, such as [Co(acac)₂(P-ligand)₂]⁺ (acac = pentane-2,4-dionate) and [Co(dtc)₂(P-ligand)₂]⁺ (dtc = N,N-dimethyldithiocarbamate). It was possible to synthesize a series of dtc complexes with diphenylphosphine (Suzuki, Iwatsuki et al., 2001), phosphites (Matsui et al., 1993), phosphonites and phosphinites (Kashiwabara et al., 2001), as well as tertiary phosphines (Suzuki, Kashiwabara et al., 2001 NOT IN REF LIST), while only tertiary phosphine complexes have been prepared for the series of acac complexes (Suzuki, Kashiwamura et al., 1998; Suzuki, Kaizaki et al., 2000). It was suggested that dtc is the best ligand to stabilize the Co^III–P bond due to its steric compactness and electronic softness (Suzuki, Kashiwamura et al., 2001).

The title compound, [Co₂(µ(S)-dtc)₂(dtc)₂{P(OMe)₂Ph}₂](PF₆)₂ (I, Scheme 1) was the unexpected product of the attempted recrystallization of trans-[Co(dtc)₂{P(OMe)₂Ph}₂]PF₆, II, in the course of which the mononuclear molecules of II each lost one phosphonite ligand thus permitting the formation of dinuclear complex I in which the Co atoms are bridged by one S of each of two dtc ligands (Fig. 1).

The coordination mode for dithiocarbamates (R₂dtc: R₂NCS₂^-) bridging two metal centers by one of the S atoms, µ₂(S)—R₂dtc-κ³S,S,S', has often been observed: the April 2001 release of the Cambridge Structural Database (Allen & Kennard, 1993) contains more than 60 reports of compounds with such an R₂dtc coordination mode. Typical examples involving bis(µ₂(S)—R₂dtc-κ³S,S,S') ligands are the dinuclear complexes composed of two edge-sharing square-pyramidal polyhedra, each of which consists of the square-planar M^II(dtc)₂ (M = Mo, Fe, Cu, Zn, Cd or Hg) moiety and an apical bridging S atom (types A1 and A2 in Scheme 2, in which bold lines represent R₂dtc chelates). [Co₂(Et₂dtc)₅]BF₄ (Hendrickson et al., 1975) is the only example within Co^III complexes, and the structure of the cation is illustrated in Scheme 2, type B; it consists of two edge-sharing octahedra, of [Co(Et₂dtc)₃] and cis-[Co(Et₂dtc)₂]⁺. This type of dinuclear species was also found for [Rh₂(dtc)₅]BF₄ (Hendrickson et al., 1976) and [Ru₂(ⁱPr₂dtc)₅]⁺ (Raston & White, 1975a). The structure of the complex cation in (I) can be categorized as type C1 in Scheme 2: two P(OMe)₂Ph ligands are sited at the transoid positions of two edge-sharing octahedra. The complex cation has C₂ symmetry, so it can be considered as a type A1 species with two monodentate ligands added. This kind of structure has already been found in [Ru₂(Et₂dtc)₄(CO)₂] (Raston & White, 1975b) and [Re₂(Et₂dtc)₄{NB(C₆F₅)₃}₂] (Abram, 1999). Interestingly, all three examples of the [M₂(µ-dtc)₂(dtc)₂L₂] structure are of type C1. There are four other possible isomers for the [M₂(µ-dtc)₂(dtc)₂L₂]-type of dinuclear complex (i.e., types C2, C3, C4 and C5), but no complex having these structures has been reported to date. Furthermore, for the related [M₂(µ-dtc)₂L₆]-type dinuclear complexes, [Pt₂(µ-dtc)₂(CH₃)₆] (Heard et al., 2000), [Ru₂(µ-dtc)₂([9]aneS₃)₂]²⁺ (Landgrafe & Sheldrick, 1994) and [Mo₂(µ-Et₂dtc)₂(CO)₄(NO)₂] (Shiu et al., 1995), all the reported structures are of type D1 rather than type D2 (Scheme 2).

The two bridging Co–S bond lengths in complex I are 2.276 (1) and 2.387 (1) Å. The latter (Co–S1ⁱ bond) is appreciably longer than those than those [2.298 (8) and 2.333 (8) Å] in [Co₂(Et₂dtc)₅]BF₄ (Hendrickson et al., 1975), suggesting that the bridge which forms the dinuclear structure is not as strong in complex I as in [Co₂(Et₂dtc)₅]BF₄. The structure of the Co(dtc)₂{P(OMe)₂Ph} moiety is similar to that of the Co(dtc)₂(PMe₂Ph)⁺ cation in trans-[Co(dtc)₂(PMe₂Ph)₂]BF₄ (Suzuki, Kashiwamura et al., 2001), the phenyl ring being located directly above one of the S atoms, S4 in complex I, with a stacking interaction to the dtc plane. The dihedral angle between the phenyl ring and the dtc mean plane is 19.6 (2)°. The S–Co–S bite angles, 77.68 (4) and 77.10 (4)°, of dtc in complex I are comparable to those in trans-[Co(dtc)₂(PMe_3-nPh_n)₂]BF₄ (Suzuki, Kashiwamura et al., 2001) and also in [Co(dtc)₃] (Iwasaki & Kobayashi, 1980).

The Co—P bond lengths in complex I are 2.192 (1) Å. There are only a few reports of structural analyses of Co^III complexes containing P(OMe)₂Ph. Except for four organometallic Co^III complexes, complex I is only the third example of such non-organometallic Co^III—P(OMe)₂Ph complexes, the other two being trans-[Co(Hdmg)₂Cl{P(OMe)₂Ph}] (Hdmg = dimethylglyoximate monoanion; Bresciani-Pahor et al., 1982) and cis-[Co(dtc)₂{P(OMe)₂Ph}₂]PF₆ (Kashiwabara et al., 2001), where the Co—P bond lengths are reported as 2.213 (2) and average 2.218 (3) Å, respectively.

S2. Experimental

Reaction of Co(BF₄)₂·6H₂O, P(OMe)₂Ph and tetramethylthiuram disulfide (molar ratio of 2:4:1) in MeOH/CH₂Cl₂ afforded cis-[Co(dtc)₂{P(OMe)₂Ph}₂]BF₄ (III). Irradiation by UV-light for 5 h of an MeOH solution of III and NH₄PF₆ afforded thin brown platey crystals of the trans-isomer, II. Repeated recrystallization of II from CH₃CN/Et₂O and then from MeOH/CH₂Cl₂ gave purple prismatic crystals of I whose ¹H NMR spectrum was consistent with the dinuclear structure. The ¹H NMR data of complex I in CD₃CN (303 K, 400 MHz) are: δ 2.852 (s, –NCH₃, 3H), 2.903 (s, –NCH₃, 3H), 3.235 (s, –NCH₃, 3H), 3.273 (s, –NCH₃, 3H), 3.825 (d, –OCH₃, J = 10.8 Hz, 3H), 3.915 (d, –OCH₃, J = 10.4 Hz, 3H), and 7.40–7.71 (m, –C₆H₅, 5H).

S3. Refinement

Methyl H atoms attached to the N atoms of the dimethyldithiocarbamate ligands were located from ΔF syntheses and refined as a part of a rigid groups which were allowed to rotate but not tip or distort, and with C—H = 0.96 Å and U_iso(H) = 1.2U_eq(C). Other H atoms were placed geometrically and refined using a riding model with C—H = 0.96 Å (for methyl H) or 0.93 Å (for phenyl H) and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: MSC/AFC Diffractometer Control (Rigaku Co. Ltd, 1985); cell refinement: MSC/AFC Diffractometer Control (Rigaku Co. Ltd, 1985); data reduction: TEXSAN ver. 1.11 (Molecular Structure Corporation and Rigaku Co. Ltd, 2000); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1970); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. A perspective view of the complex dication in (I). H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level. Symmetry code: (i) -x,y,1/2 - z.

Bis[bis(dimethyldithiocarbamato)(dimethylphenylphosphonito)cobalt(III)] Bis(hexafluorophosphate)

Crystal data

[Co(C3H6NS2)4(C8H11O2P)2]·2(PF6)	F(000) = 2496
Mr = 1228.91	Dx = 1.697 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
a = 26.454 (3) Å	Cell parameters from 24 reflections
b = 14.499 (3) Å	θ = 14.7–15.0°
c = 14.517 (3) Å	µ = 1.26 mm^−1
β = 120.276 (10)°	T = 296 K
V = 4808.8 (16) Å^3	Square prism, purple
Z = 4	0.28 × 0.26 × 0.18 mm

Data collection

Rigaku AFC5R diffractometer	3741 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.023
Graphite monochromator	θmax = 30.0°, θmin = 2.6°
ω–2θ scans	h = 0→37
Absorption correction: ψ scan (North et al., 1968)	k = 0→20
Tmin = 0.744, Tmax = 0.798	l = −20→17
7153 measured reflections	3 standard reflections every 150 reflections
7017 independent reflections	intensity decay: 1.1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: see text
wR(F^2) = 0.164	See text
S = 1.04	w = 1/[σ^2(Fo^2) + (0.082P)^2 + 1.623P] where P = (Fo^2 + 2Fc^2)/3
7017 reflections	(Δ/σ)max = 0.019
284 parameters	Δρmax = 0.94 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

Experimental. none

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co	0.06306 (2)	0.23665 (3)	0.24314 (4)	0.03142 (13)
S1	−0.03434 (4)	0.25486 (6)	0.12626 (7)	0.03358 (19)
S2	0.05701 (4)	0.38723 (6)	0.20155 (8)	0.0384 (2)
S3	0.15851 (4)	0.21982 (7)	0.36901 (8)	0.0411 (2)
S4	0.06887 (4)	0.08504 (6)	0.28897 (8)	0.0366 (2)
P1	0.08938 (4)	0.20933 (8)	0.12470 (9)	0.0417 (2)
O1	0.13616 (17)	0.2836 (2)	0.1339 (4)	0.0742 (11)
O2	0.03351 (15)	0.2163 (3)	0.0098 (3)	0.0730 (11)
N1	−0.05476 (14)	0.4364 (2)	0.0706 (3)	0.0423 (7)
N2	0.18158 (14)	0.0417 (2)	0.4250 (3)	0.0450 (8)
C1	−0.01636 (16)	0.3719 (3)	0.1245 (3)	0.0361 (7)
C2	−0.11718 (19)	0.4194 (3)	0.0130 (4)	0.0563 (12)
H2A	−0.1353	0.4561	−0.0507	0.068*
H2B	−0.1333	0.4356	0.0571	0.068*
H2C	−0.1243	0.3553	−0.0056	0.068*
C3	−0.0359 (2)	0.5329 (3)	0.0771 (4)	0.0561 (12)
H3A	−0.0491	0.5684	0.1168	0.067*
H3B	−0.0524	0.5579	0.0065	0.067*
H3C	0.0060	0.5355	0.1123	0.067*
C4	0.14212 (15)	0.1055 (3)	0.3708 (3)	0.0356 (8)
C5	0.24357 (18)	0.0643 (4)	0.4903 (4)	0.0673 (14)
H5A	0.2665	0.0092	0.5039	0.084*
H5B	0.2509	0.0903	0.5567	0.084*
H5C	0.2541	0.1081	0.4533	0.084*
C6	0.1654 (2)	−0.0551 (3)	0.4163 (4)	0.0573 (11)
H6A	0.1680	−0.0750	0.4816	0.071*
H6B	0.1916	−0.0912	0.4032	0.071*
H6C	0.1261	−0.0631	0.3584	0.071*
C7	0.1701 (3)	0.2912 (5)	0.0866 (6)	0.093 (2)
H7A	0.1904	0.2341	0.0946	0.108*
H7B	0.1981	0.3399	0.1202	0.108*
H7C	0.1455	0.3048	0.0121	0.108*
C8	0.0306 (3)	0.2033 (5)	−0.0915 (4)	0.0781 (17)
H8A	−0.0093	0.1933	−0.1462	0.093*
H8B	0.0537	0.1507	−0.0873	0.093*
H8C	0.0455	0.2572	−0.1083	0.093*
C9	0.12132 (18)	0.0983 (3)	0.1292 (3)	0.0430 (9)
C10	0.1817 (2)	0.0843 (3)	0.1883 (4)	0.0501 (10)
H10	0.2067	0.1338	0.2221	0.061*
C11	0.2046 (2)	−0.0037 (4)	0.1967 (4)	0.0697 (15)
H11	0.2448	−0.0128	0.2360	0.085*
C12	0.1685 (3)	−0.0766 (4)	0.1478 (5)	0.0803 (18)
H12	0.1841	−0.1353	0.1544	0.093*
C13	0.1082 (3)	−0.0637 (4)	0.0882 (5)	0.0803 (18)
H13	0.0837	−0.1136	0.0541	0.102*
C14	0.0850 (2)	0.0223 (4)	0.0795 (4)	0.0641 (13)
H14	0.0447	0.0304	0.0402	0.076*
P2	0.14661 (6)	0.65956 (9)	0.28257 (12)	0.0594 (3)
F1	0.1629 (3)	0.5615 (3)	0.2593 (5)	0.153 (2)
F2	0.1821 (2)	0.6980 (4)	0.2325 (5)	0.162 (2)
F3	0.2018 (3)	0.6613 (5)	0.3924 (4)	0.191 (3)
F4	0.0928 (2)	0.6543 (5)	0.1689 (4)	0.172 (3)
F5	0.1119 (4)	0.6165 (5)	0.3277 (7)	0.235 (4)
F6	0.1309 (3)	0.7550 (3)	0.3068 (5)	0.166 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0275 (2)	0.0289 (2)	0.0393 (3)	0.00133 (17)	0.0180 (2)	0.00202 (19)
S1	0.0297 (4)	0.0335 (4)	0.0381 (4)	0.0015 (3)	0.0175 (4)	−0.0001 (3)
S2	0.0361 (5)	0.0323 (5)	0.0496 (5)	−0.0002 (3)	0.0237 (4)	0.0040 (4)
S3	0.0289 (4)	0.0372 (5)	0.0518 (6)	−0.0021 (3)	0.0163 (4)	0.0015 (4)
S4	0.0304 (4)	0.0319 (4)	0.0478 (5)	−0.0006 (3)	0.0199 (4)	0.0020 (4)
P1	0.0384 (5)	0.0458 (6)	0.0488 (6)	0.0074 (4)	0.0278 (5)	0.0058 (4)
O1	0.090 (3)	0.0493 (19)	0.131 (3)	0.0104 (18)	0.092 (3)	0.018 (2)
O2	0.055 (2)	0.123 (3)	0.0419 (17)	0.033 (2)	0.0248 (16)	0.0108 (19)
N1	0.0393 (17)	0.0428 (18)	0.0463 (18)	0.0092 (14)	0.0228 (15)	0.0091 (14)
N2	0.0307 (15)	0.0468 (19)	0.053 (2)	0.0033 (13)	0.0182 (15)	0.0110 (15)
C1	0.0375 (18)	0.0346 (18)	0.0415 (19)	0.0032 (14)	0.0239 (16)	0.0033 (15)
C2	0.043 (2)	0.062 (3)	0.057 (3)	0.015 (2)	0.020 (2)	0.008 (2)
C3	0.068 (3)	0.038 (2)	0.072 (3)	0.012 (2)	0.043 (3)	0.015 (2)
C4	0.0296 (17)	0.0382 (18)	0.043 (2)	0.0010 (14)	0.0208 (16)	0.0048 (15)
C5	0.030 (2)	0.074 (3)	0.079 (4)	0.007 (2)	0.015 (2)	0.023 (3)
C6	0.056 (3)	0.041 (2)	0.073 (3)	0.012 (2)	0.031 (2)	0.016 (2)
C7	0.086 (4)	0.083 (4)	0.140 (6)	0.017 (3)	0.080 (5)	0.038 (4)
C8	0.074 (4)	0.118 (5)	0.048 (3)	0.022 (3)	0.036 (3)	0.009 (3)
C9	0.044 (2)	0.044 (2)	0.050 (2)	−0.0022 (17)	0.0305 (19)	−0.0042 (17)
C10	0.048 (2)	0.044 (2)	0.068 (3)	0.0026 (18)	0.036 (2)	0.0018 (19)
C11	0.079 (4)	0.063 (3)	0.080 (4)	0.028 (3)	0.049 (3)	0.020 (3)
C12	0.128 (6)	0.047 (3)	0.098 (5)	0.017 (3)	0.081 (5)	0.006 (3)
C13	0.120 (6)	0.056 (3)	0.096 (4)	−0.028 (3)	0.078 (4)	−0.029 (3)
C14	0.067 (3)	0.062 (3)	0.078 (3)	−0.020 (2)	0.047 (3)	−0.021 (3)
P2	0.0570 (7)	0.0516 (7)	0.0704 (8)	−0.0039 (6)	0.0327 (7)	0.0018 (6)
F1	0.204 (6)	0.093 (3)	0.187 (5)	0.037 (4)	0.117 (5)	−0.005 (3)
F2	0.149 (5)	0.181 (6)	0.188 (6)	−0.059 (4)	0.108 (4)	0.016 (4)
F3	0.150 (5)	0.238 (8)	0.095 (3)	0.029 (5)	−0.006 (3)	−0.020 (4)
F4	0.087 (3)	0.282 (8)	0.105 (3)	0.035 (4)	0.016 (3)	−0.049 (4)
F5	0.368 (11)	0.198 (7)	0.316 (9)	−0.145 (7)	0.304 (9)	−0.089 (6)
F6	0.181 (6)	0.080 (3)	0.213 (6)	0.032 (3)	0.082 (5)	−0.035 (3)

Geometric parameters (Å, º)

Co—P1	2.1921 (11)	C5—H5B	0.9600
Co—S1	2.2757 (10)	C5—H5C	0.9600
Co—S2	2.2493 (11)	C6—H6A	0.9600
Co—S3	2.2633 (11)	C6—H6B	0.9600
Co—S4	2.2793 (11)	C6—H6C	0.9600
Co—S1^i	2.3865 (11)	C7—H7A	0.9600
S1—C1	1.766 (4)	C7—H7B	0.9600
S2—C1	1.696 (4)	C7—H7C	0.9600
S3—C4	1.716 (4)	C8—H8A	0.9600
S4—C4	1.713 (4)	C8—H8B	0.9600
P1—O1	1.594 (4)	C8—H8C	0.9600
P1—O2	1.578 (3)	C9—C10	1.396 (6)
P1—C9	1.804 (4)	C9—C14	1.399 (6)
O1—C7	1.384 (6)	C10—C11	1.390 (6)
O2—C8	1.446 (6)	C10—H10	0.9300
N1—C1	1.310 (5)	C11—C12	1.360 (8)
N1—C2	1.447 (5)	C11—H11	0.9300
N1—C3	1.473 (5)	C12—C13	1.390 (9)
N2—C4	1.318 (5)	C12—H12	0.9300
N2—C6	1.455 (6)	C13—C14	1.368 (8)
N2—C5	1.458 (5)	C13—H13	0.9300
C2—H2A	0.9600	C14—H14	0.9300
C2—H2B	0.9600	P2—F1	1.571 (5)
C2—H2C	0.9600	P2—F2	1.552 (5)
C3—H3A	0.9600	P2—F3	1.526 (5)
C3—H3B	0.9600	P2—F4	1.544 (5)
C3—H3C	0.9600	P2—F5	1.505 (5)
C5—H5A	0.9600	P2—F6	1.536 (4)
P1—Co—S2	88.43 (4)	H5A—C5—H5B	109.5
P1—Co—S3	86.99 (4)	N2—C5—H5C	109.5
S2—Co—S3	102.76 (4)	H5A—C5—H5C	109.5
P1—Co—S1	97.13 (4)	H5B—C5—H5C	109.5
S2—Co—S1	77.68 (4)	N2—C6—H6A	109.5
S3—Co—S1	175.88 (4)	N2—C6—H6B	109.5
P1—Co—S4	93.06 (4)	H6A—C6—H6B	109.5
S2—Co—S4	178.49 (4)	N2—C6—H6C	109.5
S3—Co—S4	77.10 (4)	H6A—C6—H6C	109.5
S1—Co—S4	102.35 (4)	H6B—C6—H6C	109.5
P1—Co—S1^i	175.94 (4)	O1—C7—H7A	109.5
S2—Co—S1^i	95.61 (4)	O1—C7—H7B	109.5
S3—Co—S1^i	92.47 (4)	H7A—C7—H7B	109.5
S1—Co—S1^i	83.41 (4)	O1—C7—H7C	109.5
S4—Co—S1^i	82.90 (4)	H7A—C7—H7C	109.5
C1—S1—Co	84.86 (12)	H7B—C7—H7C	109.5
C1—S1—Co^i	108.26 (12)	O2—C8—H8A	109.5
Co—S1—Co^i	95.11 (4)	O2—C8—H8B	109.5
C1—S2—Co	87.30 (13)	H8A—C8—H8B	109.5
C4—S3—Co	85.92 (12)	O2—C8—H8C	109.5
C4—S4—Co	85.49 (13)	H8A—C8—H8C	109.5
O2—P1—O1	108.6 (2)	H8B—C8—H8C	109.5
O2—P1—C9	105.5 (2)	C10—C9—C14	118.5 (4)
O1—P1—C9	105.66 (18)	C10—C9—P1	121.5 (3)
O2—P1—Co	108.59 (13)	C14—C9—P1	119.8 (4)
O1—P1—Co	110.63 (15)	C11—C10—C9	120.0 (5)
C9—P1—Co	117.46 (14)	C11—C10—H10	120.0
C7—O1—P1	133.1 (4)	C9—C10—H10	120.0
C8—O2—P1	127.4 (3)	C12—C11—C10	120.5 (5)
C1—N1—C2	122.6 (4)	C12—C11—H11	119.7
C1—N1—C3	120.3 (4)	C10—C11—H11	119.7
C2—N1—C3	116.7 (4)	C11—C12—C13	120.2 (5)
C4—N2—C6	121.1 (3)	C11—C12—H12	119.9
C4—N2—C5	121.6 (4)	C13—C12—H12	119.9
C6—N2—C5	117.2 (4)	C14—C13—C12	120.0 (5)
N1—C1—S2	125.8 (3)	C14—C13—H13	120.0
N1—C1—S1	124.1 (3)	C12—C13—H13	120.0
S2—C1—S1	110.1 (2)	C13—C14—C9	120.7 (5)
N1—C2—H2A	109.5	C13—C14—H14	119.6
N1—C2—H2B	109.5	C9—C14—H14	119.6
H2A—C2—H2B	109.5	F1—P2—F2	85.9 (3)
N1—C2—H2C	109.5	F1—P2—F3	91.0 (4)
H2A—C2—H2C	109.5	F1—P2—F4	86.0 (3)
H2B—C2—H2C	109.5	F1—P2—F5	90.7 (4)
N1—C3—H3A	109.5	F1—P2—F6	179.3 (4)
N1—C3—H3B	109.5	F2—P2—F3	89.8 (4)
H3A—C3—H3B	109.5	F2—P2—F4	88.1 (3)
N1—C3—H3C	109.5	F2—P2—F5	176.4 (4)
H3A—C3—H3C	109.5	F2—P2—F6	94.7 (4)
H3B—C3—H3C	109.5	F3—P2—F4	176.5 (4)
N2—C4—S4	124.8 (3)	F3—P2—F5	91.4 (5)
N2—C4—S3	123.8 (3)	F3—P2—F6	88.5 (3)
S4—C4—S3	111.3 (2)	F4—P2—F5	90.5 (5)
N2—C5—H5A	109.5	F4—P2—F6	94.5 (3)
N2—C5—H5B	109.5	F5—P2—F6	88.8 (4)
P1—Co—S1—C1	−88.81 (13)	O1—P1—O2—C8	59.8 (5)
S2—Co—S1—C1	−1.99 (12)	C9—P1—O2—C8	−53.1 (5)
S4—Co—S1—C1	176.46 (12)	Co—P1—O2—C8	−179.9 (5)
S1^i—Co—S1—C1	95.25 (12)	C2—N1—C1—S2	−175.2 (3)
P1—Co—S1—Co^i	163.26 (4)	C3—N1—C1—S2	−2.6 (6)
S2—Co—S1—Co^i	−109.92 (4)	C2—N1—C1—S1	5.2 (6)
S4—Co—S1—Co^i	68.53 (4)	C3—N1—C1—S1	177.7 (3)
S1^i—Co—S1—Co^i	−12.68 (5)	Co—S2—C1—N1	177.6 (3)
P1—Co—S2—C1	99.71 (13)	Co—S2—C1—S1	−2.77 (17)
S3—Co—S2—C1	−173.73 (13)	Co—S1—C1—N1	−177.6 (3)
S1—Co—S2—C1	2.07 (13)	Co^i—S1—C1—N1	−83.9 (3)
S1^i—Co—S2—C1	−79.91 (13)	Co—S1—C1—S2	2.75 (17)
P1—Co—S3—C4	−90.95 (13)	Co^i—S1—C1—S2	96.44 (18)
S2—Co—S3—C4	−178.66 (13)	C6—N2—C4—S4	1.9 (6)
S4—Co—S3—C4	2.88 (13)	C5—N2—C4—S4	177.9 (4)
S1^i—Co—S3—C4	85.02 (13)	C6—N2—C4—S3	−175.0 (3)
P1—Co—S4—C4	83.31 (13)	C5—N2—C4—S3	1.0 (6)
S3—Co—S4—C4	−2.89 (13)	Co—S4—C4—N2	−173.2 (3)
S1—Co—S4—C4	−178.70 (13)	Co—S4—C4—S3	3.99 (18)
S1^i—Co—S4—C4	−97.08 (13)	Co—S3—C4—N2	173.2 (3)
S2—Co—P1—O2	−75.36 (18)	Co—S3—C4—S4	−4.02 (18)
S3—Co—P1—O2	−178.22 (18)	O2—P1—C9—C10	147.3 (4)
S1—Co—P1—O2	2.02 (19)	O1—P1—C9—C10	32.3 (4)
S4—Co—P1—O2	104.88 (18)	Co—P1—C9—C10	−91.6 (4)
S2—Co—P1—O1	43.72 (16)	O2—P1—C9—C14	−37.8 (4)
S3—Co—P1—O1	−59.14 (16)	O1—P1—C9—C14	−152.8 (4)
S1—Co—P1—O1	121.10 (16)	Co—P1—C9—C14	83.3 (4)
S4—Co—P1—O1	−136.04 (16)	C14—C9—C10—C11	0.1 (7)
S2—Co—P1—C9	165.11 (16)	P1—C9—C10—C11	175.0 (4)
S3—Co—P1—C9	62.24 (16)	C9—C10—C11—C12	−0.1 (8)
S1—Co—P1—C9	−117.52 (16)	C10—C11—C12—C13	0.5 (9)
S4—Co—P1—C9	−14.66 (16)	C11—C12—C13—C14	−0.8 (9)
O2—P1—O1—C7	−68.7 (6)	C12—C13—C14—C9	0.8 (8)
C9—P1—O1—C7	44.1 (6)	C10—C9—C14—C13	−0.4 (7)
Co—P1—O1—C7	172.2 (5)	P1—C9—C14—C13	−175.5 (4)

Symmetry code: (i) −x, y, −z+1/2.