trans-(4-Amino-2,2,6,6-tetramethyl­piperidine-N⁴)bis(pentane-2,4-dion­ato-O,O')(triphenylphosphine-P)cobalt(III) hexafluorophosphate dichloromethane solvate

The complex cation in the title compound, [Co(C₅H₇O₂)₂(C₉H₂₀N₂)(C₁₈H₁₅P)]PF₆·CH₂Cl₂, is the first example of a Co^III complex in which a trans configuration for the coordinated monodentate phosphine and amine ligands has been confirmed by X-ray analysis. Owing to the large steric bulkiness of the axial PPh₃ ligands influencing the interaction with the equatorial acetyl­acetonate ligands, the acetyl­acetonate planes bend away considerably from the PPh₃ ligands.

S1. Comment

In previous studies we have reported that trans-[Co(acac)₂(PPh₃)₂]⁺ (Hacac = acetylacetone) is highly reactive toward substitution of the coordinated PPh₃. For example, the reactions with strong Lewis bases such as PMe₃ and CN^- stereoselectively gave trans-[Co(acac)₂(PMe₃)₂]⁺ and trans-[Co(acac)₂(CN)₂]^-, respectively (Suzuki et al., 1998). Further, the reaction with an equimolar amount of substituted pyridine or amine derivatives (N-ligands) in CH₂Cl₂ afforded trans-[Co(acac)₂(PPh₃)(N-ligand)]⁺ in an almost quantitative yield (Ogita et al., 2000). These complexes are novel examples of Co^III complexes in which monodentate phosphine and amine ligands are located in the trans position (Katoh et al., 1984), and there has been no X-ray analysis for such complexes. Here, we report the single-crystal structure determination of the title complex, (I), which is the reaction product with 4-amino-2,2,6,6-tetramethylpiperidine (atmp). \scheme

The X-ray analysis confirmed the trans configuration for the phosphine and amine ligands in the cation of (I) (Fig. 1), as suggested by NMR spectroscopy in a CDCl₃ solution. The most remarkable structural feature of the cation in (I) is the bending of the equatorial acac ligand planes away from the axial PPh₃. The bending angles of the acac plane 1 (defined by O1, O2, C2, C3 and C4) and acac plane 2 (defined by O3, O4, C7, C8 and C9) from the equatorial four-oxygen coordination plane (defined by O1, O2, O3 and O4) are 9.8 (3) and 11.5 (3)°, respectively. The dihedral angle between the two acac planes is 21.2 (3)°. Such a bending structure was also found in trans-[Co(acac)₂(PPh₃)(H₂O)]PF₆ (Suzuki et al., 1999) and trans-[Co(acac)₂(PPh₃)(NIT4py or IM4py)]PF₆ (Ogita et al., 2000), and resulted from the large steric bulkiness of the axial PPh₃ influencing the interaction with the equatorial acac ligands. The three phenyl rings [phenyl(1) C11–C16, phenyl(2) C17–C22 and phenyl(3) C23–C28] of PPh₃ have dihedral angles of 17.1 (3), 44.3 (2) and 75.6 (3)°, respectively, with the equatorial four-oxygen coordination plane. The other structural parameters concerning the Co^III-acac moiety are normal; the Co—O bond lengths are in the range 1.872 (4)–1.897 (4) Å and the acac bite angles (O—Co—O) are 95.0 (2) and 94.6 (2)°. These lengths and angles are similar to those in trans-[Co(acac)₂(CN)₂]^-, trans-[Co(acac)₂(PPh₃)₂]⁺ (Suzuki et al., 1999) and [Co(acac)₃] (Kruger & Reynhardt, 1974).

In the cation of (I), the atmp ligand is coordinated to Co^III through the primary amine (N1), and the Co—N1 bond length is 2.014 (5) Å. This is, to our best knowledge, the first X-ray structural analysis of metal complexes containing atmp, while for its oxidized nitroxide radical, 4-amino-2,2,6,6-tetramethylpiperidinyl-1-oxide (amino-TEMPO), a crystal structure of the Ni^II complex, trans-[Ni(hfac)₂(amino-TEMPO)(CH₃OH)] (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate), has already been reported (Cervantes-Lee & Porter, 1991). In (I), the six-membered piperidine ring of atmp adopts an ideal chair conformation and the coordinated amino group is in an equatorial position. The piperidyl group is oriented toward the void between two acac ligands, the torsion angle of the bisector of O1—Co—O4 and the N1—C29 with respect to Co—N1 bond, i.e. X—Co—N1—C29, where X is the midpoint of O1···O4, being only 4.7°. This orientation would effectively minimize the steric interaction between the piperidyl group and the bent acac planes.

The Co—P bond length in (I) is 2.292 (2) Å, which is shorter by ca 0.1 Å than that (2.3887 Å) in trans-[Co(acac)₂(PPh₃)₂]PF₆ (Suzuki et al., 1999). Since in trans-[Co(acac)₂(PPh₃)₂]PF₆ the steric interaction between two PPh₃ and acac ligands occurs at both sides of the equatorial four-oxygen coordination plane, the substitution of one of the PPh₃ ligands by atmp may give rise to a reduction in this steric interaction on one side. As a result, shortening of the remaining Co-PPh₃ bond is induced, which causes the bending of the acac planes. There have been a huge number of X-ray structural analyses of Co^III complexes containing PPh₃ or the other monodentate tertiary phosphines. Although the many cobaloxime derivatives containing a tertiary phosphine have been analyzed (Bresciani-Pahor et al., 1985), most of them have an anionic ligand or an organic group at the trans position to the phosphine, and no complexes with neutral N-ligand such as pyridines or amines have been reported so far. The Co—P bond lengths in the cobaloxime derivatives vary from 2.286 to 2.460 Å, depending on the type of trans-positioned ligand. As an example, the Co—P bond length in the structurally related 3,5-di-butylcatecholate monoanion (3,5-DBcatH) complex, trans-[Co(Hdmg)₂(PPh₃)(3,5-DBcatH)] (Hdmg = dimethylglyoximate monoanion), is 2.316 (1) Å (Simándi et al., 1995).

S2. Experimental

Compound (I) was prepared by a reaction of trans-[Co(acac)₂(PPh₃)₂]PF₆ and atmp (molar ratio 1:1) in CH₂Cl₂ at room temperature, precipitated by adding Et₂O and recrystallized from CH₂Cl₂/Et₂O (yield 77%). Analysis found: C 50.22, H 5.68, N 3.12%; calculated for C₃₈H₅₁Cl₂CoF₆N₂O₄P₂: C 50.40, H 5.68, N 3.09%.

S3. Refinement

The F atoms of the PF₆^- anion were found to be positionally disordered and assumed to be three sets of arrangements with occupancies of 1/2, 0.25 and 1/4, because an attempt to refine the occupancies gave values close to these. These six F atoms were refined isotropically. Coordinates of all H atoms were refined with a fixed bond length, except for those of –CH₃ which were assumed as idealized tetrahedral arrangements.

Computing details

Data collection: Rigaku/AFC Diffractometer Control Software (Rigaku Corporation, 1985); cell refinement: Rigaku/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation and Rigaku Corporation, 1999); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP (Johnson, 1970); software used to prepare material for publication: TEXSAN.

Figures

Fig. 1. A perspective view of the complex cation in (I). H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 40% probability level.

trans-(4-Amino-2,2,6,6-tetramethylpiperidine-N⁴)bis(pentane-2,4-dionato-O,O') (triphenylphosphine-P)cobalt(III) hexafluorophosphate dichloromethane solvate

Crystal data

[Co(C5H7O2)2(C18H15P)(C9H20N2)]PF6·CH2Cl2	Dx = 1.352 Mg m^−3
Mr = 905.61	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 15.169 (10) Å	θ = 11.1–12.4°
b = 25.197 (8) Å	µ = 0.64 mm^−1
c = 11.638 (6) Å	T = 296 K
V = 4448 (3) Å^3	Plate, dark red
Z = 4	0.32 × 0.28 × 0.13 mm
F(000) = 1880

Data collection

Rigaku AFC-5R diffractometer	Rint = 0.022
ω/2θ scans	θmax = 30.0°
Absorption correction: integration (Coppens et al., 1965)	h = −9→21
Tmin = 0.843, Tmax = 0.922	k = 0→35
9217 measured reflections	l = −7→16
7522 independent reflections	3 standard reflections every 150 reflections
3148 reflections with F > 4σ(F)	intensity decay: 2.0%

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.193	(Δ/σ)max = 0.031
S = 0.97	Δρmax = 0.45 e Å^−3
7522 reflections	Δρmin = −0.52 e Å^−3
518 parameters	Absolute structure: Flack (1983)
27 restraints	Absolute structure parameter: −0.01 (3)

Special details

Geometry. the angles between least-squares planes: plane 1 defined by O1, O2, O3, O4. plane 2 defined by O1, O2, C2, C3, C4. plane 3 defined by O3, O4, C7, C8, C9. plane 4 defined by C11, C12, C13, C14, C15, C16. plane 5 defined by C17, C18, C19, C20, C21, C22. plane 6 defined by C23, C24, C25, C26, C27, C28. plane 1 versus plane 2 = 9.8 (3)° plane 1 versus plane 3 = 11.5 (3)° plane 2 versus plane 3 = 21.2 (3)° plane 1 versus plane 4 = 17.1 (2)° plane 1 versus plane 5 = 44.2 (3)° plane 1 versus plane 6 = 75.6 (3)° plane 2 versus plane 4 = 24.0 (4)°

Refinement. None

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	−0.01063 (5)	0.65085 (3)	0.12375 (7)	0.0340 (2)
Cl1	0.0673 (3)	0.6535 (2)	0.6334 (3)	0.152 (2)
Cl2	−0.1032 (2)	0.6155 (2)	0.6846 (3)	0.161 (2)
P1	−0.0223 (1)	0.56021 (7)	0.1177 (2)	0.0435 (4)
P2	0.4883 (2)	0.67704 (9)	0.1375 (2)	0.0554 (5)
F11	0.4188 (8)	0.6310 (5)	0.167 (1)	0.06128 (4)*	0.50
F12	0.5609 (6)	0.7174 (4)	0.0897 (9)	0.05929 (3)*	0.50
F13	0.4166 (7)	0.6958 (5)	0.0401 (10)	0.06839 (4)*	0.50
F14	0.5458 (8)	0.6674 (6)	0.246 (1)	0.08298 (5)*	0.50
F15	0.548 (1)	0.6391 (7)	0.067 (2)	0.11391 (6)*	0.50
F16	0.4259 (10)	0.7142 (6)	0.213 (1)	0.10320 (5)*	0.50
F21	0.420 (2)	0.656 (1)	0.228 (2)	0.08499 (9)*	0.25
F22	0.558 (2)	0.686 (1)	0.036 (2)	0.07651 (8)*	0.25
F23	0.429 (1)	0.7259 (7)	0.117 (2)	0.15603 (8)*	0.50
F24	0.546 (2)	0.710 (1)	0.231 (3)	0.1142 (1)*	0.25
F25	0.546 (1)	0.6212 (8)	0.145 (2)	0.07404 (8)*	0.25
F26	0.439 (1)	0.6662 (7)	0.016 (2)	0.04762 (5)*	0.25
F31	0.429 (2)	0.624 (1)	0.126 (2)	0.0816 (1)*	0.25
F32	0.535 (1)	0.7331 (7)	0.131 (2)	0.05337 (6)*	0.25
F34	0.564 (1)	0.6427 (9)	0.204 (2)	0.05448 (6)*	0.25
F35	0.510 (2)	0.656 (1)	0.009 (2)	0.09510 (9)*	0.25
F36	0.460 (2)	0.690 (1)	0.261 (2)	0.1020 (1)*	0.25
O1	−0.0912 (3)	0.6470 (2)	0.2454 (4)	0.041 (1)
O2	−0.0966 (3)	0.6605 (2)	0.0098 (4)	0.042 (1)
O3	0.0703 (3)	0.6541 (2)	−0.0004 (4)	0.043 (1)
O4	0.0771 (3)	0.6470 (2)	0.2375 (4)	0.041 (1)
N1	−0.0039 (3)	0.7305 (2)	0.1362 (4)	0.041 (1)
N2	−0.0143 (4)	0.8454 (2)	0.4022 (5)	0.048 (1)
C1	−0.2237 (5)	0.6482 (4)	0.3467 (7)	0.081 (3)
C2	−0.1733 (5)	0.6547 (4)	0.2370 (7)	0.053 (2)
C3	−0.2164 (4)	0.6698 (3)	0.1351 (9)	0.062 (2)
C4	−0.1778 (5)	0.6708 (3)	0.0291 (7)	0.050 (2)
C5	−0.2324 (5)	0.6862 (4)	−0.0742 (8)	0.073 (3)
C6	0.2017 (5)	0.6708 (4)	−0.0995 (7)	0.078 (3)
C7	0.1527 (5)	0.6628 (3)	0.0107 (7)	0.050 (2)
C8	0.1968 (4)	0.6636 (3)	0.1160 (8)	0.058 (2)
C9	0.1589 (4)	0.6535 (4)	0.2206 (7)	0.052 (2)
C10	0.2146 (5)	0.6525 (4)	0.3264 (7)	0.074 (3)
C11	−0.1381 (5)	0.5409 (3)	0.0991 (8)	0.056 (2)
C12	−0.1857 (6)	0.5217 (4)	0.1927 (8)	0.069 (3)
C13	−0.2722 (7)	0.5143 (5)	0.181 (1)	0.104 (4)
C14	−0.3173 (6)	0.5240 (5)	0.082 (1)	0.101 (4)
C15	−0.2724 (7)	0.5412 (5)	−0.013 (1)	0.098 (4)
C16	−0.1822 (6)	0.5516 (4)	−0.0041 (8)	0.070 (3)
C17	0.0395 (6)	0.5270 (3)	0.0055 (8)	0.062 (2)
C18	−0.0034 (8)	0.4928 (4)	−0.0748 (9)	0.097 (4)
C19	0.047 (1)	0.4685 (6)	−0.158 (1)	0.130 (6)
C20	0.136 (1)	0.4762 (6)	−0.162 (1)	0.146 (7)
C21	0.1787 (8)	0.5080 (5)	−0.085 (1)	0.127 (5)
C22	0.1290 (7)	0.5328 (4)	0.0020 (10)	0.090 (3)
C23	0.0132 (5)	0.5261 (3)	0.2495 (6)	0.048 (2)
C24	0.0121 (6)	0.5515 (3)	0.3558 (6)	0.057 (2)
C25	0.0332 (7)	0.5230 (3)	0.4536 (7)	0.069 (3)
C26	0.0541 (7)	0.4705 (4)	0.4491 (9)	0.080 (3)
C27	0.0519 (8)	0.4453 (4)	0.345 (1)	0.097 (4)
C28	0.0331 (7)	0.4716 (4)	0.2457 (8)	0.076 (3)
C29	−0.0050 (5)	0.7570 (2)	0.2503 (5)	0.039 (1)
C30	−0.0909 (5)	0.7865 (3)	0.2722 (7)	0.048 (2)
C31	0.0716 (4)	0.7947 (3)	0.2624 (6)	0.045 (2)
C32	−0.0943 (5)	0.8128 (3)	0.3886 (7)	0.052 (2)
C33	0.0728 (4)	0.8229 (3)	0.3803 (8)	0.049 (2)
C34	−0.1703 (5)	0.8526 (4)	0.3900 (8)	0.076 (3)
C35	−0.1087 (6)	0.7732 (4)	0.4836 (6)	0.069 (3)
C36	0.1371 (5)	0.8702 (4)	0.3721 (9)	0.089 (3)
C37	0.1065 (6)	0.7853 (4)	0.4711 (8)	0.078 (3)
C38	−0.0175 (8)	0.6546 (5)	0.7269 (9)	0.123 (5)
H1A	−0.195 (2)	0.667 (2)	0.407 (1)	0.0814*
H01A	0.0438	0.7403	0.0999	0.0411*
H1B	−0.227 (3)	0.6113 (5)	0.366 (2)	0.0814*
H01B	−0.0497	0.7429	0.0954	0.0411*
H1C	−0.282 (1)	0.662 (2)	0.337 (1)	0.0814*
H02	−0.0219	0.8724	0.3550	0.0484*
H3	−0.2775	0.6799	0.1438	0.0617*
H5A	−0.204 (2)	0.715 (1)	−0.114 (2)	0.0726*
H5B	−0.290 (1)	0.697 (2)	−0.0495 (8)	0.0726*
H5C	−0.238 (3)	0.6563 (6)	−0.125 (2)	0.0726*
H6A	0.192 (3)	0.6409 (10)	−0.149 (2)	0.0780*
H6B	0.2636 (6)	0.674 (2)	−0.0838 (9)	0.0780*
H6C	0.181 (2)	0.703 (1)	−0.136 (2)	0.0780*
H8	0.2590	0.6704	0.1150	0.0584*
H10A	0.272 (1)	0.639 (2)	0.308 (1)	0.0738*
H10B	0.188 (2)	0.630 (1)	0.383 (2)	0.0738*
H10C	0.219 (3)	0.6877 (5)	0.357 (2)	0.0738*
H12	−0.1543	0.5162	0.2658	0.0694*
H13	−0.3069	0.4999	0.2456	0.1042*
H14	−0.3831	0.5213	0.0809	0.1013*
H15	−0.3026	0.5458	−0.0878	0.0981*
H16	−0.1495	0.5668	−0.0663	0.0701*
H18	−0.0683	0.4864	−0.0679	0.0972*
H19	0.0178	0.4470	−0.2180	0.1302*
H20	0.1630	0.4548	−0.2216	0.1461*
H21	0.2411	0.5144	−0.0986	0.1271*
H22	0.1591	0.5541	0.0651	0.0904*
H24	−0.0076	0.5882	0.3609	0.0573*
H25	0.0362	0.5408	0.5279	0.0691*
H26	0.0719	0.4509	0.5189	0.0803*
H27	0.0640	0.4079	0.3445	0.0973*
H28	0.0316	0.4529	0.1718	0.0764*
H29	0.0002	0.7304	0.3095	0.0392*
H30A	−0.0982	0.8133	0.2136	0.0477*
H30B	−0.1402	0.7623	0.2643	0.0477*
H31A	0.0657	0.8229	0.2018	0.0449*
H31B	0.1259	0.7781	0.2487	0.0449*
H34A	−0.2253 (5)	0.8339 (4)	0.395 (4)	0.0763*
H34B	−0.169 (2)	0.873 (1)	0.321 (2)	0.0763*
H34C	−0.164 (2)	0.876 (1)	0.455 (3)	0.0763*
H35A	−0.070 (2)	0.7434 (9)	0.473 (2)	0.0689*
H35B	−0.169 (1)	0.761 (1)	0.482 (3)	0.0689*
H35C	−0.096 (3)	0.7896 (7)	0.5562 (7)	0.0689*
H36A	0.117 (2)	0.894 (1)	0.314 (3)	0.0888*
H36B	0.1947 (9)	0.8574 (4)	0.352 (4)	0.0888*
H36C	0.140 (3)	0.888 (1)	0.445 (2)	0.0888*
H37A	0.097 (3)	0.8005 (10)	0.5458 (8)	0.0776*
H37B	0.1684 (9)	0.779 (2)	0.460 (3)	0.0776*
H37C	0.076 (2)	0.7521 (8)	0.466 (3)	0.0776*
H38A	0.0038	0.6431	0.8018	0.1228*
H38B	−0.0371	0.6907	0.7361	0.1228*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0303 (4)	0.0398 (4)	0.0318 (4)	−0.0019 (4)	0.0006 (4)	−0.0038 (4)
Cl1	0.138 (3)	0.200 (4)	0.117 (3)	−0.044 (3)	0.032 (3)	−0.008 (3)
Cl2	0.109 (3)	0.235 (5)	0.139 (3)	−0.048 (3)	0.013 (2)	−0.080 (3)
P1	0.0446 (10)	0.0425 (9)	0.0434 (10)	−0.0035 (8)	0.000 (1)	−0.0067 (9)
P2	0.051 (1)	0.063 (1)	0.053 (1)	0.002 (1)	0.003 (1)	0.003 (1)
O1	0.031 (2)	0.049 (3)	0.044 (3)	−0.001 (2)	0.010 (2)	0.000 (3)
O2	0.042 (3)	0.047 (3)	0.037 (3)	0.000 (2)	−0.006 (2)	−0.003 (2)
O3	0.032 (2)	0.058 (3)	0.038 (3)	−0.006 (2)	0.005 (2)	−0.010 (3)
O4	0.039 (3)	0.049 (3)	0.036 (3)	−0.002 (2)	−0.004 (2)	0.000 (3)
N1	0.046 (3)	0.040 (3)	0.037 (3)	−0.002 (3)	0.005 (3)	0.000 (2)
N2	0.054 (3)	0.036 (3)	0.055 (4)	−0.002 (3)	−0.004 (3)	−0.006 (3)
C1	0.057 (5)	0.101 (7)	0.086 (7)	−0.016 (5)	0.036 (5)	−0.026 (7)
C2	0.041 (4)	0.057 (5)	0.061 (5)	−0.008 (4)	0.018 (4)	−0.006 (5)
C3	0.028 (3)	0.077 (6)	0.081 (6)	0.002 (3)	0.001 (4)	−0.016 (5)
C4	0.039 (4)	0.055 (5)	0.056 (5)	−0.006 (4)	−0.014 (4)	−0.001 (4)
C5	0.047 (5)	0.087 (7)	0.083 (7)	0.006 (5)	−0.027 (4)	0.007 (6)
C6	0.054 (5)	0.118 (9)	0.062 (6)	−0.010 (5)	0.022 (4)	−0.007 (5)
C7	0.041 (4)	0.055 (5)	0.053 (5)	−0.002 (4)	0.011 (4)	−0.009 (4)
C8	0.026 (3)	0.085 (6)	0.065 (5)	−0.008 (3)	0.003 (4)	−0.007 (5)
C9	0.031 (4)	0.063 (5)	0.062 (5)	0.007 (4)	−0.008 (3)	−0.016 (5)
C10	0.048 (5)	0.104 (8)	0.069 (6)	0.016 (5)	−0.021 (4)	−0.006 (6)
C11	0.053 (4)	0.045 (4)	0.070 (6)	−0.013 (4)	−0.011 (4)	−0.007 (4)
C12	0.058 (5)	0.064 (6)	0.086 (7)	−0.017 (5)	0.000 (5)	0.002 (5)
C13	0.066 (7)	0.12 (1)	0.12 (1)	−0.038 (7)	−0.002 (7)	0.012 (8)
C14	0.053 (6)	0.110 (9)	0.14 (1)	−0.036 (6)	−0.017 (7)	0.008 (8)
C15	0.072 (7)	0.114 (9)	0.108 (9)	−0.021 (6)	−0.036 (7)	−0.017 (8)
C16	0.077 (6)	0.068 (6)	0.065 (6)	−0.022 (5)	−0.017 (5)	−0.023 (5)
C17	0.079 (7)	0.050 (5)	0.057 (5)	0.008 (5)	0.006 (5)	−0.001 (4)
C18	0.126 (9)	0.081 (7)	0.085 (6)	0.042 (7)	−0.028 (7)	−0.044 (5)
C19	0.17 (1)	0.11 (1)	0.11 (1)	0.04 (1)	0.00 (1)	−0.056 (9)
C20	0.21 (2)	0.11 (1)	0.12 (1)	0.06 (1)	0.07 (1)	−0.016 (9)
C21	0.12 (1)	0.095 (10)	0.16 (1)	0.026 (8)	0.08 (1)	−0.018 (9)
C22	0.083 (7)	0.091 (8)	0.097 (9)	0.007 (6)	0.020 (7)	−0.016 (7)
C23	0.036 (4)	0.050 (4)	0.058 (5)	0.007 (4)	−0.007 (4)	0.008 (3)
C24	0.078 (5)	0.048 (4)	0.047 (4)	0.008 (4)	−0.004 (5)	0.007 (3)
C25	0.106 (8)	0.052 (5)	0.049 (5)	−0.013 (5)	0.005 (5)	0.006 (4)
C26	0.092 (8)	0.077 (7)	0.072 (7)	0.002 (6)	0.001 (6)	0.024 (6)
C27	0.121 (9)	0.056 (6)	0.115 (10)	0.034 (6)	−0.005 (8)	0.020 (6)
C28	0.097 (7)	0.052 (5)	0.081 (7)	0.012 (5)	0.000 (6)	−0.002 (5)
C29	0.045 (4)	0.042 (4)	0.031 (3)	−0.003 (3)	−0.003 (3)	−0.004 (3)
C30	0.040 (4)	0.049 (5)	0.054 (5)	−0.006 (4)	−0.001 (4)	−0.008 (4)
C31	0.035 (4)	0.052 (5)	0.048 (5)	−0.008 (3)	−0.003 (3)	−0.007 (4)
C32	0.047 (4)	0.062 (5)	0.046 (5)	0.005 (4)	0.003 (4)	−0.026 (4)
C33	0.040 (4)	0.055 (5)	0.051 (5)	−0.005 (3)	−0.004 (4)	−0.008 (5)
C34	0.061 (5)	0.096 (7)	0.072 (6)	0.011 (5)	0.014 (5)	−0.023 (6)
C35	0.089 (7)	0.083 (7)	0.034 (5)	−0.012 (5)	0.019 (4)	0.000 (5)
C36	0.042 (4)	0.105 (8)	0.120 (8)	−0.028 (5)	−0.006 (6)	−0.050 (7)
C37	0.058 (6)	0.107 (8)	0.068 (6)	−0.007 (5)	−0.011 (5)	−0.023 (6)
C38	0.117 (10)	0.18 (1)	0.074 (7)	−0.050 (10)	0.015 (7)	−0.038 (8)

Geometric parameters (Å, º)

Co—P1	2.292 (2)	C6—H6A	0.960
Co—O1	1.872 (4)	C6—H6B	0.960
Co—O2	1.875 (5)	C6—H6C	0.960
Co—O3	1.897 (4)	C8—H8	0.959
Co—O4	1.880 (4)	C10—H10A	0.960
Co—N1	2.014 (5)	C10—H10B	0.960
P1—C11	1.836 (8)	C10—H10C	0.960
P1—C17	1.812 (9)	C12—H12	0.985
P1—C23	1.839 (8)	C13—H13	0.985
O1—C2	1.265 (9)	C14—H14	1.001
O2—C4	1.279 (9)	C15—H15	0.993
O3—C7	1.276 (9)	C16—H16	0.958
O4—C9	1.266 (8)	C18—H18	1.000
N1—C29	1.486 (8)	C19—H19	0.994
N2—C32	1.474 (9)	C20—H20	0.974
N2—C33	1.460 (9)	C21—H21	0.973
C1—C2	1.50 (1)	C22—H22	1.018
C2—C3	1.41 (1)	C24—H24	0.973
C3—C4	1.37 (1)	C25—H25	0.975
C4—C5	1.51 (1)	C26—H26	0.990
C6—C7	1.50 (1)	C27—H27	0.961
C7—C8	1.40 (1)	C28—H28	0.981
C8—C9	1.37 (1)	C29—H29	0.964
C9—C10	1.49 (1)	C30—H30A	0.967
C11—C12	1.39 (1)	C30—H30B	0.969
C11—C16	1.40 (1)	C31—H31A	1.006
C12—C13	1.33 (1)	C31—H31B	0.936
C13—C14	1.36 (2)	C34—H34A	0.960
C14—C15	1.37 (2)	C34—H34B	0.960
C15—C16	1.40 (1)	C34—H34C	0.960
C17—C18	1.43 (1)	C35—H35A	0.960
C17—C22	1.37 (1)	C35—H35B	0.960
C18—C19	1.37 (2)	C35—H35C	0.960
C19—C20	1.37 (3)	C36—H36A	0.960
C20—C21	1.36 (2)	C36—H36B	0.960
C21—C22	1.41 (2)	C36—H36C	0.960
C23—C24	1.39 (1)	C37—H37A	0.960
C23—C28	1.41 (1)	C37—H37B	0.960
C24—C25	1.38 (1)	C37—H37C	0.960
C25—C26	1.36 (1)	Cl1—C38	1.68 (1)
C26—C27	1.37 (2)	Cl2—C38	1.70 (1)
C27—C28	1.36 (2)	C38—H38A	0.974
C29—C30	1.52 (1)	C38—H38B	0.962
C29—C31	1.507 (10)	P2—F11	1.61 (1)
C30—C32	1.51 (1)	P2—F12	1.60 (1)
C31—C33	1.54 (1)	P2—F13	1.64 (1)
C32—C34	1.53 (1)	P2—F14	1.55 (1)
C32—C35	1.50 (1)	P2—F15	1.55 (2)
C33—C36	1.54 (1)	P2—F16	1.59 (2)
C33—C37	1.51 (1)	P2—F21	1.56 (3)
N1—H01A	0.873	P2—F22	1.60 (2)
N1—H01B	0.898	P2—F23	1.55 (2)
N2—H02	0.881	P2—F24	1.63 (3)
C1—H1A	0.960	P2—F25	1.66 (2)
C1—H1B	0.960	P2—F26	1.62 (2)
C1—H1C	0.960	P2—F31	1.61 (3)
C3—H3	0.967	P2—F32	1.58 (2)
C5—H5A	0.960	P2—F34	1.63 (2)
C5—H5B	0.960	P2—F35	1.62 (3)
C5—H5C	0.960	P2—F36	1.53 (3)
P1—Co—O1	85.5 (2)	C13—C12—H12	122.9
P1—Co—O2	93.1 (2)	C12—C13—H13	120.2
P1—Co—O3	94.0 (2)	C14—C13—H13	116.1
P1—Co—O4	91.4 (2)	C13—C14—H14	120.3
P1—Co—N1	177.2 (2)	C15—C14—H14	120.1
O1—Co—O2	95.0 (2)	C14—C15—H15	121.2
O1—Co—O3	179.3 (2)	C16—C15—H15	119.6
O1—Co—O4	85.8 (2)	C11—C16—H16	118.5
O1—Co—N1	91.7 (2)	C15—C16—H16	121.8
O2—Co—O3	84.6 (2)	C17—C18—H18	119.5
O2—Co—O4	175.5 (2)	C19—C18—H18	122.2
O2—Co—N1	87.5 (2)	C18—C19—H19	119.4
O3—Co—O4	94.6 (2)	C20—C19—H19	119.8
O3—Co—N1	88.8 (2)	C19—C20—H20	111.0
O4—Co—N1	88.0 (2)	C21—C20—H20	126.7
Co—P1—C11	109.9 (2)	C20—C21—H21	117.1
Co—P1—C17	116.2 (3)	C22—C21—H21	124.1
Co—P1—C23	114.7 (2)	C17—C22—H22	118.7
C11—P1—C17	106.7 (4)	C21—C22—H22	120.9
C11—P1—C23	104.8 (4)	C23—C24—H24	119.6
C17—P1—C23	103.5 (4)	C25—C24—H24	120.9
Co—O1—C2	125.2 (5)	C24—C25—H25	120.1
Co—O2—C4	124.9 (5)	C26—C25—H25	118.1
Co—O3—C7	124.4 (5)	C25—C26—H26	121.2
Co—O4—C9	125.3 (5)	C27—C26—H26	120.2
Co—N1—C29	120.8 (4)	C26—C27—H27	116.9
C32—N2—C33	120.6 (6)	C28—C27—H27	121.1
O1—C2—C1	114.9 (7)	C23—C28—H28	119.5
O1—C2—C3	124.3 (7)	C27—C28—H28	120.8
C1—C2—C3	120.8 (7)	N1—C29—H29	109.0
C2—C3—C4	124.6 (7)	C30—C29—H29	106.8
O2—C4—C3	124.6 (7)	C31—C29—H29	107.9
O2—C4—C5	116.1 (7)	C29—C30—H30A	108.7
C3—C4—C5	119.3 (7)	C29—C30—H30B	109.7
O3—C7—C6	115.0 (7)	C32—C30—H30A	108.8
O3—C7—C8	124.1 (7)	C32—C30—H30B	109.6
C6—C7—C8	120.9 (7)	H30A—C30—H30B	106.5
C7—C8—C9	125.2 (6)	C29—C31—H31A	108.1
O4—C9—C8	125.0 (7)	C29—C31—H31B	112.3
O4—C9—C10	115.1 (7)	C33—C31—H31A	107.4
C8—C9—C10	119.8 (6)	C33—C31—H31B	110.3
P1—C11—C12	119.7 (7)	H31A—C31—H31B	106.0
P1—C11—C16	120.5 (6)	C32—C34—H34A	109.5
C12—C11—C16	119.3 (8)	C32—C34—H34B	109.5
C11—C12—C13	118.8 (9)	C32—C34—H34C	109.5
C12—C13—C14	123 (1)	H34A—C34—H34B	109.5
C13—C14—C15	119.4 (9)	H34A—C34—H34C	109.5
C14—C15—C16	119 (1)	H34B—C34—H34C	109.5
C11—C16—C15	119.6 (9)	C32—C35—H35A	109.5
P1—C17—C18	121.0 (7)	C32—C35—H35B	109.5
P1—C17—C22	119.1 (7)	C32—C35—H35C	109.5
C18—C17—C22	119.8 (9)	H35A—C35—H35B	109.5
C17—C18—C19	118 (1)	H35A—C35—H35C	109.5
C18—C19—C20	120 (1)	H35B—C35—H35C	109.5
C19—C20—C21	122 (1)	C33—C36—H36A	109.5
C20—C21—C22	118 (1)	C33—C36—H36B	109.5
C17—C22—C21	120 (1)	C33—C36—H36C	109.5
P1—C23—C24	121.5 (6)	H36A—C36—H36B	109.5
P1—C23—C28	119.5 (6)	H36A—C36—H36C	109.5
C24—C23—C28	118.6 (7)	H36B—C36—H36C	109.5
C23—C24—C25	119.3 (7)	C33—C37—H37A	109.5
C24—C25—C26	121.8 (8)	C33—C37—H37B	109.5
C25—C26—C27	118.6 (9)	C33—C37—H37C	109.5
C26—C27—C28	122.0 (9)	H37A—C37—H37B	109.5
C23—C28—C27	119.6 (9)	H37A—C37—H37C	109.5
N1—C29—C30	112.3 (5)	H37B—C37—H37C	109.5
N1—C29—C31	111.0 (5)	Cl1—C38—Cl2	112.7 (6)
C30—C29—C31	109.7 (6)	Cl1—C38—H38A	108.6
C29—C30—C32	113.2 (6)	Cl1—C38—H38B	109.0
C29—C31—C33	112.4 (6)	Cl2—C38—H38A	109.8
N2—C32—C30	108.2 (6)	Cl2—C38—H38B	110.0
N2—C32—C34	104.7 (6)	H38A—C38—H38B	106.5
N2—C32—C35	114.2 (6)	F11—P2—F12	170.7 (6)
C30—C32—C34	108.8 (6)	F11—P2—F13	85.6 (6)
C30—C32—C35	111.9 (7)	F11—P2—F14	94.6 (7)
C34—C32—C35	108.5 (7)	F11—P2—F15	92.9 (8)
N2—C33—C31	108.9 (6)	F11—P2—F16	85.2 (7)
N2—C33—C36	106.4 (6)	F12—P2—F13	91.9 (6)
N2—C33—C37	115.4 (7)	F12—P2—F14	89.7 (6)
C31—C33—C36	107.9 (7)	F12—P2—F15	78.9 (7)
C31—C33—C37	109.7 (7)	F12—P2—F16	103.1 (7)
C36—C33—C37	108.3 (7)	F13—P2—F14	168.3 (7)
Co—N1—H01A	106.8	F13—P2—F15	101.2 (8)
Co—N1—H01B	105.6	F13—P2—F16	79.4 (7)
C29—N1—H01A	108.3	F14—P2—F15	90.5 (8)
C29—N1—H01B	107.9	F14—P2—F16	88.9 (8)
H01A—N1—H01B	106.6	F15—P2—F16	177.9 (8)
C32—N2—H02	104.7	F21—P2—F22	168 (1)
C33—N2—H02	108.1	F21—P2—F23	88 (1)
C2—C1—H1A	109.5	F21—P2—F24	94 (1)
C2—C1—H1B	109.5	F21—P2—F25	91 (1)
C2—C1—H1C	109.5	F21—P2—F26	102 (1)
H1A—C1—H1B	109.5	F22—P2—F23	99 (1)
H1A—C1—H1C	109.5	F22—P2—F24	93 (1)
H1B—C1—H1C	109.5	F22—P2—F25	79 (1)
C2—C3—H3	115.3	F22—P2—F26	71 (1)
C4—C3—H3	120.1	F23—P2—F24	90 (1)
C4—C5—H5A	109.5	F23—P2—F25	172 (1)
C4—C5—H5B	109.5	F23—P2—F26	74 (1)
C4—C5—H5C	109.5	F23—P2—F31	108 (1)
H5A—C5—H5B	109.5	F23—P2—F32	62.8 (9)
H5A—C5—H5C	109.5	F23—P2—F34	154 (1)
H5B—C5—H5C	109.5	F23—P2—F35	103 (1)
C7—C6—H6A	109.5	F23—P2—F36	78 (1)
C7—C6—H6B	109.5	F24—P2—F25	96 (1)
C7—C6—H6C	109.5	F24—P2—F26	156 (1)
H6A—C6—H6B	109.5	F25—P2—F26	98 (1)
H6A—C6—H6C	109.5	F31—P2—F32	169 (1)
H6B—C6—H6C	109.5	F31—P2—F34	89 (1)
C7—C8—H8	117.6	F31—P2—F35	76 (1)
C9—C8—H8	117.2	F31—P2—F36	95 (1)
C9—C10—H10A	109.5	F32—P2—F34	100 (1)
C9—C10—H10B	109.5	F32—P2—F35	98 (1)
C9—C10—H10C	109.5	F32—P2—F36	88 (1)
H10A—C10—H10B	109.5	F34—P2—F35	97 (1)
H10A—C10—H10C	109.5	F34—P2—F36	82 (1)
H10B—C10—H10C	109.5	F35—P2—F36	172 (1)
C11—C12—H12	118.2