(2.2.2-Cryptand)potassium tetra­carbonyl­cobaltate(−I)

Brennessel, W.W.; Ellis, J.E.

doi:10.1107/S1600536814006758

metal-organic compounds

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Volume 70| Part 5| May 2014| Page m180

doi:10.1107/S1600536814006758

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(2.2.2-Cryptand)potassium tetracarbonylcobaltate(−I)

William W. Brennessel ^a ^* and John E. Ellis ^a

^aDepartment of Chemistry, 207 Pleasant Street SE, University of Minnesota, Minneapolis, MN 55455, USA
^*Correspondence e-mail: brennessel@chem.rochester.edu

(Received 19 March 2014; accepted 26 March 2014; online 16 April 2014)

The title salt, [K(C₁₈H₃₆N₂O₆)][Co(CO)₄], is an example of a classical carbonylmetalate. The asymmetric unit contains one cation and one tetrahedral anion, both in general positions. Based on comparison of the four carbonyl C—O bond lengths and C—Co—C angles, the anion is unperturbed by the cation, which is normal for an alkali metal fully encased by a cryptand cage.

CCDC reference: 993915

Related literature

For a survey of metal carbonyl anions, see: Ellis (2003 ). For the synthesis of the precursor bis(anthracene)cobaltate, see: Brennessel et al. (2002 ). For an in-depth discussion of the perturbations of the title anion by cations in various solvents, as measured by IR spectroscopy, see: Edgell & Lyford (1971 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[K(C₁₈H₃₆N₂O₆)][Co(CO)₄]
M_r = 586.56
Monoclinic, P 2₁ /c
a = 9.3611 (18) Å
b = 12.022 (2) Å
c = 25.358 (5) Å
β = 91.536 (4)°
V = 2852.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 173 K
0.30 × 0.19 × 0.14 mm

Data collection

Bruker SMART CCD platform diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2012 ) T_min = 0.521, T_max = 0.745
14351 measured reflections
5046 independent reflections
3551 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.093
S = 0.92
5046 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—C4	1.762 (3)
Co1—C3	1.763 (4)
Co1—C1	1.767 (3)
Co1—C2	1.770 (4)

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 993915

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814006758/nk2222sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814006758/nk2222Isup2.hkl

checkCIF report

Comment top

The title salt (Fig. 1) contains the classical metal carbonyl anion (Ellis, 2003) tetracarbonylcobaltate, which has now appeared in the Cambridge Structural Database (CSD, Version 5.35, update No. 2, Febuary 2014, Allen, 2002) 86 times, 70 for which it serves simply as an anion of modest bulk, as in the title salt. In eleven instances it is part of an alkali metal or thallium network, and in the remaining five occurrences it is coordinated through an oxygen atom to a transition metal or lanthanide.

Because the cobaltate is an unperturbed anion in this salt, the IR stretch is very strong and without features, as expected for a tetrahedron. In contrast, the very strong IR stretch of K[Co(CO)₄] in instances in which there can be monodentate or tridentate K···O interactions has a shoulder that is due to symmetry reduction from T_d to C_3v (Edgell & Lyford, 1971).

Related literature top

For a survey of metal carbonyl anions, see: Ellis (2003). For the synthesis of the precursor bis(anthracene)cobaltate, see: Brennessel et al. (2002). For an in-depth discussion of the perturbations of the title anion by cations in various solvents, as measured by IR spectroscopy, see: Edgell & Lyford (1971). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Argon was removed under vacuum from a deep pinkish-red solution of [K([2.2.2]cryptand)][Co(η⁴-C₁₄H₁₀)₂]·0.5THF (Brennessel et al., 2002) stirring in tetrahydrofuran (THF) at room temperature. Carbon monoxide (1 atm) was added, and the solution became immediately colorless. After a few minutes, the carbon monoxide and most of the solvent were removed under vacuum. Argon was reintroduced and diethyl ether was added to extract the anthracene and to precipitate the product. After filtering, washing (diethyl ether), and drying, the colorless salt was obtained in quantitative yield.

IR (νCO, THF, cm^-1): 1892 vs; IR (νCO, Nujol mull, cm^-1): 1878 vs br; ⁵⁹Co NMR (71.15 MHz, CD₃CN, 293 K, external reference 0.1 M K₃[Co(CN)₆] in D₂O at 0.0 p.p.m., δ, p.p.m.): -3015.7 (s). Colorless blocks were grown from a pentane-layered THF solution at 273 K.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title salt, showing the atom numbering. Displacement ellipsoids are drawn at the 50% probability level.

(2.2.2-Cryptand)potassium tetracarbonylcobaltate(-I) top

Crystal data top

[K(C₁₈H₃₆N₂O₆)][Co(CO)₄]	F(000) = 1232
M_r = 586.56	D_x = 1.366 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3611 (18) Å	Cell parameters from 3996 reflections
b = 12.022 (2) Å	θ = 2.3–24.6°
c = 25.358 (5) Å	µ = 0.80 mm⁻¹
β = 91.536 (4)°	T = 173 K
V = 2852.8 (9) Å³	Block, colorless
Z = 4	0.30 × 0.19 × 0.14 mm

Data collection top

Bruker SMART CCD platform diffractometer	3551 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	R_int = 0.058
ω scans	θ_max = 25.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2012)	h = −11→11
T_min = 0.521, T_max = 0.745	k = −11→14
14351 measured reflections	l = −29→30
5046 independent reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.0428P)²] where P = (F_o² + 2F_c²)/3
5046 reflections	(Δ/σ)_max < 0.001
325 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[K(C₁₈H₃₆N₂O₆)][Co(CO)₄]	V = 2852.8 (9) Å³
M_r = 586.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3611 (18) Å	µ = 0.80 mm⁻¹
b = 12.022 (2) Å	T = 173 K
c = 25.358 (5) Å	0.30 × 0.19 × 0.14 mm
β = 91.536 (4)°

Data collection top

Bruker SMART CCD platform diffractometer	5046 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2012)	3551 reflections with I > 2σ(I)
T_min = 0.521, T_max = 0.745	R_int = 0.058
14351 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 0.92	Δρ_max = 0.39 e Å⁻³
5046 reflections	Δρ_min = −0.23 e Å⁻³
325 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Co1	0.03175 (4)	0.80932 (3)	0.38562 (2)	0.03777 (12)
C1	0.1014 (3)	0.8470 (2)	0.44858 (12)	0.0452 (7)
O1	0.1456 (3)	0.8706 (2)	0.48980 (8)	0.0653 (6)
C2	−0.1456 (4)	0.8597 (3)	0.37998 (11)	0.0489 (8)
O2	−0.2606 (3)	0.8925 (2)	0.37675 (10)	0.0736 (7)
C3	0.0336 (3)	0.6631 (3)	0.38061 (11)	0.0462 (7)
O3	0.0358 (2)	0.56731 (19)	0.37816 (9)	0.0651 (6)
C4	0.1381 (3)	0.8663 (2)	0.33608 (11)	0.0436 (7)
O4	0.2078 (3)	0.90302 (17)	0.30383 (8)	0.0627 (6)
K1	0.37979 (6)	0.39030 (5)	0.37685 (2)	0.03466 (15)
N1	0.2667 (2)	0.17944 (18)	0.42354 (9)	0.0408 (6)
C5	0.2462 (3)	0.1981 (2)	0.48042 (11)	0.0488 (8)
H5A	0.3399	0.1921	0.4992	0.059*
H5B	0.1837	0.1387	0.4940	0.059*
C6	0.1812 (3)	0.3093 (3)	0.49271 (11)	0.0520 (8)
H6A	0.0928	0.3201	0.4710	0.062*
H6B	0.1558	0.3120	0.5303	0.062*
O5	0.28056 (19)	0.39546 (15)	0.48182 (7)	0.0399 (5)
C7	0.2248 (3)	0.5016 (2)	0.49582 (11)	0.0482 (8)
H7A	0.2008	0.5019	0.5336	0.058*
H7B	0.1364	0.5170	0.4748	0.058*
C8	0.3322 (3)	0.5887 (2)	0.48574 (11)	0.0504 (8)
H8A	0.2952	0.6621	0.4965	0.060*
H8B	0.4208	0.5733	0.5067	0.060*
O6	0.3626 (2)	0.58999 (15)	0.43112 (7)	0.0438 (5)
C9	0.4473 (3)	0.6823 (2)	0.41678 (12)	0.0512 (8)
H9A	0.5469	0.6716	0.4299	0.061*
H9B	0.4096	0.7511	0.4328	0.061*
C10	0.4439 (3)	0.6927 (2)	0.35785 (12)	0.0535 (8)
H10A	0.3437	0.7042	0.3456	0.064*
H10B	0.4988	0.7597	0.3481	0.064*
C11	0.1280 (3)	0.1528 (2)	0.39757 (12)	0.0481 (8)
H11A	0.0532	0.2005	0.4126	0.058*
H11B	0.1034	0.0745	0.4052	0.058*
C12	0.1278 (3)	0.1691 (2)	0.33879 (12)	0.0492 (8)
H12A	0.2091	0.1285	0.3237	0.059*
H12B	0.0383	0.1392	0.3227	0.059*
O7	0.13939 (19)	0.28435 (15)	0.32733 (7)	0.0396 (5)
C13	0.1274 (3)	0.3049 (3)	0.27216 (10)	0.0480 (8)
H13A	0.0340	0.2776	0.2582	0.058*
H13B	0.2040	0.2650	0.2537	0.058*
C14	0.1397 (3)	0.4268 (3)	0.26271 (11)	0.0461 (7)
H14A	0.1179	0.4437	0.2251	0.055*
H14B	0.0707	0.4674	0.2845	0.055*
O8	0.28281 (19)	0.46132 (16)	0.27640 (7)	0.0458 (5)
C15	0.3056 (3)	0.5738 (3)	0.26203 (12)	0.0610 (9)
H15A	0.2431	0.6231	0.2825	0.073*
H15B	0.2822	0.5843	0.2241	0.073*
C16	0.4602 (3)	0.6026 (3)	0.27332 (12)	0.0619 (9)
H16A	0.5212	0.5508	0.2535	0.074*
H16B	0.4786	0.6787	0.2603	0.074*
C17	0.3671 (3)	0.0864 (2)	0.41663 (13)	0.0509 (8)
H17A	0.3546	0.0569	0.3804	0.061*
H17B	0.3429	0.0261	0.4414	0.061*
C18	0.5219 (3)	0.1185 (3)	0.42583 (12)	0.0507 (8)
H18A	0.5350	0.1519	0.4613	0.061*
H18B	0.5831	0.0515	0.4241	0.061*
O9	0.56202 (19)	0.19592 (16)	0.38686 (7)	0.0466 (5)
C19	0.7118 (3)	0.2156 (2)	0.38849 (11)	0.0473 (8)
H19A	0.7635	0.1451	0.3823	0.057*
H19B	0.7417	0.2442	0.4237	0.057*
C20	0.7477 (3)	0.2982 (2)	0.34723 (11)	0.0471 (8)
H20A	0.8527	0.3074	0.3461	0.056*
H20B	0.7129	0.2716	0.3123	0.056*
O10	0.68266 (18)	0.40194 (15)	0.35896 (7)	0.0404 (5)
C21	0.7229 (3)	0.4842 (2)	0.32179 (11)	0.0504 (8)
H21A	0.6887	0.4625	0.2860	0.060*
H21B	0.8284	0.4905	0.3216	0.060*
C22	0.6590 (3)	0.5936 (2)	0.33652 (12)	0.0472 (7)
H22A	0.6855	0.6102	0.3738	0.057*
H22B	0.7005	0.6526	0.3144	0.057*
N2	0.5018 (2)	0.5968 (2)	0.33005 (9)	0.0432 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0357 (2)	0.0434 (2)	0.0341 (2)	−0.00146 (18)	0.00036 (16)	0.00340 (17)
C1	0.0456 (19)	0.0426 (17)	0.0476 (18)	−0.0042 (14)	0.0054 (15)	0.0106 (14)
O1	0.0779 (17)	0.0789 (17)	0.0382 (12)	−0.0091 (13)	−0.0153 (11)	0.0002 (11)
C2	0.053 (2)	0.0490 (18)	0.0451 (17)	−0.0006 (16)	0.0038 (16)	−0.0033 (14)
O2	0.0462 (15)	0.0820 (19)	0.0924 (18)	0.0188 (13)	−0.0037 (13)	−0.0085 (14)
C3	0.0390 (18)	0.061 (2)	0.0384 (16)	−0.0029 (15)	−0.0038 (13)	−0.0001 (15)
O3	0.0783 (17)	0.0451 (14)	0.0711 (15)	−0.0066 (12)	−0.0143 (13)	−0.0077 (12)
C4	0.0494 (19)	0.0424 (17)	0.0386 (16)	0.0051 (14)	−0.0055 (14)	0.0010 (14)
O4	0.0755 (16)	0.0628 (15)	0.0510 (13)	−0.0019 (12)	0.0223 (12)	0.0182 (11)
K1	0.0300 (3)	0.0400 (3)	0.0340 (3)	−0.0031 (3)	0.0000 (2)	−0.0008 (3)
N1	0.0344 (13)	0.0383 (13)	0.0495 (14)	−0.0043 (11)	0.0000 (11)	0.0027 (11)
C5	0.0470 (19)	0.054 (2)	0.0457 (16)	−0.0079 (15)	0.0046 (14)	0.0111 (15)
C6	0.049 (2)	0.064 (2)	0.0440 (17)	−0.0022 (17)	0.0151 (15)	0.0043 (16)
O5	0.0345 (11)	0.0454 (12)	0.0400 (10)	0.0021 (9)	0.0076 (8)	0.0007 (9)
C7	0.0464 (19)	0.059 (2)	0.0395 (16)	0.0137 (16)	0.0123 (14)	−0.0012 (15)
C8	0.061 (2)	0.0461 (18)	0.0443 (17)	0.0148 (16)	0.0032 (15)	−0.0119 (14)
O6	0.0429 (12)	0.0415 (11)	0.0472 (11)	−0.0025 (9)	0.0035 (9)	−0.0040 (9)
C9	0.0429 (18)	0.0385 (17)	0.072 (2)	−0.0015 (14)	0.0036 (16)	−0.0074 (16)
C10	0.0372 (18)	0.0449 (18)	0.078 (2)	−0.0054 (15)	0.0016 (16)	0.0192 (17)
C11	0.0353 (18)	0.0441 (17)	0.065 (2)	−0.0064 (14)	−0.0034 (15)	0.0063 (15)
C12	0.0429 (19)	0.0422 (19)	0.0618 (19)	−0.0042 (14)	−0.0080 (15)	−0.0065 (15)
O7	0.0400 (11)	0.0412 (11)	0.0373 (10)	−0.0036 (9)	−0.0043 (8)	−0.0040 (8)
C13	0.0459 (19)	0.061 (2)	0.0364 (15)	−0.0009 (15)	−0.0063 (13)	−0.0111 (15)
C14	0.0403 (18)	0.063 (2)	0.0344 (15)	−0.0039 (15)	−0.0097 (13)	−0.0002 (14)
O8	0.0368 (12)	0.0596 (13)	0.0406 (11)	−0.0091 (9)	−0.0085 (9)	0.0089 (10)
C15	0.053 (2)	0.074 (2)	0.0551 (19)	−0.0184 (18)	−0.0204 (16)	0.0281 (17)
C16	0.053 (2)	0.079 (2)	0.0531 (19)	−0.0237 (18)	−0.0061 (16)	0.0281 (18)
C17	0.049 (2)	0.0367 (17)	0.067 (2)	−0.0009 (14)	−0.0008 (16)	0.0014 (15)
C18	0.0392 (18)	0.0495 (19)	0.0630 (19)	0.0065 (15)	−0.0036 (15)	0.0050 (16)
O9	0.0327 (12)	0.0509 (12)	0.0559 (12)	0.0042 (9)	−0.0032 (9)	0.0025 (10)
C19	0.0298 (16)	0.057 (2)	0.0546 (18)	0.0092 (14)	−0.0013 (14)	−0.0140 (15)
C20	0.0313 (16)	0.061 (2)	0.0489 (17)	0.0050 (14)	0.0073 (13)	−0.0147 (15)
O10	0.0291 (10)	0.0511 (12)	0.0413 (10)	0.0019 (9)	0.0092 (8)	−0.0063 (9)
C21	0.0365 (17)	0.065 (2)	0.0501 (18)	−0.0096 (15)	0.0127 (14)	−0.0038 (16)
C22	0.0329 (17)	0.057 (2)	0.0522 (17)	−0.0137 (14)	0.0038 (14)	0.0079 (15)
N2	0.0323 (13)	0.0560 (16)	0.0413 (13)	−0.0086 (12)	−0.0004 (11)	0.0091 (12)

Geometric parameters (Å, º) top

Co1—C4	1.762 (3)	C11—H11A	0.9900
Co1—C3	1.763 (4)	C11—H11B	0.9900
Co1—C1	1.767 (3)	C12—O7	1.420 (3)
Co1—C2	1.770 (4)	C12—H12A	0.9900
C1—O1	1.149 (3)	C12—H12B	0.9900
C2—O2	1.147 (3)	O7—C13	1.422 (3)
C3—O3	1.153 (4)	C13—C14	1.490 (4)
C4—O4	1.148 (3)	C13—H13A	0.9900
K1—O6	2.7741 (19)	C13—H13B	0.9900
K1—O8	2.8137 (18)	C14—O8	1.436 (3)
K1—O5	2.8433 (18)	C14—H14A	0.9900
K1—O7	2.8481 (19)	C14—H14B	0.9900
K1—O10	2.8866 (19)	O8—C15	1.418 (3)
K1—O9	2.900 (2)	C15—C16	1.508 (4)
K1—N2	2.991 (2)	C15—H15A	0.9900
K1—N1	3.003 (2)	C15—H15B	0.9900
N1—C17	1.474 (4)	C16—N2	1.482 (4)
N1—C11	1.475 (3)	C16—H16A	0.9900
N1—C5	1.477 (3)	C16—H16B	0.9900
C5—C6	1.505 (4)	C17—C18	1.512 (4)
C5—H5A	0.9900	C17—H17A	0.9900
C5—H5B	0.9900	C17—H17B	0.9900
C6—O5	1.424 (3)	C18—O9	1.416 (3)
C6—H6A	0.9900	C18—H18A	0.9900
C6—H6B	0.9900	C18—H18B	0.9900
O5—C7	1.427 (3)	O9—C19	1.421 (3)
C7—C8	1.478 (4)	C19—C20	1.488 (4)
C7—H7A	0.9900	C19—H19A	0.9900
C7—H7B	0.9900	C19—H19B	0.9900
C8—O6	1.421 (3)	C20—O10	1.423 (3)
C8—H8A	0.9900	C20—H20A	0.9900
C8—H8B	0.9900	C20—H20B	0.9900
O6—C9	1.417 (3)	O10—C21	1.424 (3)
C9—C10	1.499 (4)	C21—C22	1.497 (4)
C9—H9A	0.9900	C21—H21A	0.9900
C9—H9B	0.9900	C21—H21B	0.9900
C10—N2	1.464 (4)	C22—N2	1.477 (3)
C10—H10A	0.9900	C22—H22A	0.9900
C10—H10B	0.9900	C22—H22B	0.9900
C11—C12	1.503 (4)

C4—Co1—C3	109.24 (13)	C12—C11—H11A	109.0
C4—Co1—C1	110.01 (13)	N1—C11—H11B	109.0
C3—Co1—C1	108.48 (13)	C12—C11—H11B	109.0
C4—Co1—C2	110.86 (13)	H11A—C11—H11B	107.8
C3—Co1—C2	110.27 (14)	O7—C12—C11	109.4 (2)
C1—Co1—C2	107.94 (13)	O7—C12—H12A	109.8
O1—C1—Co1	179.1 (3)	C11—C12—H12A	109.8
O2—C2—Co1	179.4 (3)	O7—C12—H12B	109.8
O3—C3—Co1	178.9 (3)	C11—C12—H12B	109.8
O4—C4—Co1	179.7 (3)	H12A—C12—H12B	108.2
O6—K1—O8	99.49 (6)	C12—O7—C13	111.5 (2)
O6—K1—O5	59.46 (5)	C12—O7—K1	114.18 (15)
O8—K1—O5	137.33 (6)	C13—O7—K1	113.37 (15)
O6—K1—O7	123.37 (6)	O7—C13—C14	109.0 (2)
O8—K1—O7	60.31 (5)	O7—C13—H13A	109.9
O5—K1—O7	98.53 (5)	C14—C13—H13A	109.9
O6—K1—O10	96.11 (5)	O7—C13—H13B	109.9
O8—K1—O10	97.90 (5)	C14—C13—H13B	109.9
O5—K1—O10	119.53 (5)	H13A—C13—H13B	108.3
O7—K1—O10	136.07 (5)	O8—C14—C13	108.8 (2)
O6—K1—O9	134.08 (6)	O8—C14—H14A	109.9
O8—K1—O9	119.90 (6)	C13—C14—H14A	109.9
O5—K1—O9	98.15 (5)	O8—C14—H14B	109.9
O7—K1—O9	97.71 (6)	C13—C14—H14B	109.9
O10—K1—O9	58.33 (5)	H14A—C14—H14B	108.3
O6—K1—N2	60.43 (6)	C15—O8—C14	111.1 (2)
O8—K1—N2	60.42 (6)	C15—O8—K1	118.35 (16)
O5—K1—N2	119.41 (6)	C14—O8—K1	114.04 (14)
O7—K1—N2	120.12 (6)	O8—C15—C16	108.7 (3)
O10—K1—N2	60.68 (6)	O8—C15—H15A	110.0
O9—K1—N2	118.26 (6)	C16—C15—H15A	110.0
O6—K1—N1	120.61 (6)	O8—C15—H15B	110.0
O8—K1—N1	120.30 (6)	C16—C15—H15B	110.0
O5—K1—N1	61.43 (6)	H15A—C15—H15B	108.3
O7—K1—N1	60.89 (6)	N2—C16—C15	113.5 (2)
O10—K1—N1	117.46 (6)	N2—C16—H16A	108.9
O9—K1—N1	59.87 (6)	C15—C16—H16A	108.9
N2—K1—N1	178.13 (7)	N2—C16—H16B	108.9
C17—N1—C11	109.8 (2)	C15—C16—H16B	108.9
C17—N1—C5	109.3 (2)	H16A—C16—H16B	107.7
C11—N1—C5	109.4 (2)	N1—C17—C18	113.5 (2)
C17—N1—K1	111.16 (16)	N1—C17—H17A	108.9
C11—N1—K1	108.83 (16)	C18—C17—H17A	108.9
C5—N1—K1	108.26 (16)	N1—C17—H17B	108.9
N1—C5—C6	113.6 (2)	C18—C17—H17B	108.9
N1—C5—H5A	108.8	H17A—C17—H17B	107.7
C6—C5—H5A	108.8	O9—C18—C17	109.3 (2)
N1—C5—H5B	108.8	O9—C18—H18A	109.8
C6—C5—H5B	108.8	C17—C18—H18A	109.8
H5A—C5—H5B	107.7	O9—C18—H18B	109.8
O5—C6—C5	109.7 (2)	C17—C18—H18B	109.8
O5—C6—H6A	109.7	H18A—C18—H18B	108.3
C5—C6—H6A	109.7	C18—O9—C19	111.7 (2)
O5—C6—H6B	109.7	C18—O9—K1	115.11 (15)
C5—C6—H6B	109.7	C19—O9—K1	116.48 (16)
H6A—C6—H6B	108.2	O9—C19—C20	109.4 (2)
C6—O5—C7	110.9 (2)	O9—C19—H19A	109.8
C6—O5—K1	113.40 (15)	C20—C19—H19A	109.8
C7—O5—K1	112.52 (14)	O9—C19—H19B	109.8
O5—C7—C8	109.6 (2)	C20—C19—H19B	109.8
O5—C7—H7A	109.8	H19A—C19—H19B	108.2
C8—C7—H7A	109.8	O10—C20—C19	109.4 (2)
O5—C7—H7B	109.8	O10—C20—H20A	109.8
C8—C7—H7B	109.8	C19—C20—H20A	109.8
H7A—C7—H7B	108.2	O10—C20—H20B	109.8
O6—C8—C7	109.3 (2)	C19—C20—H20B	109.8
O6—C8—H8A	109.8	H20A—C20—H20B	108.2
C7—C8—H8A	109.8	C20—O10—C21	110.4 (2)
O6—C8—H8B	109.8	C20—O10—K1	114.71 (15)
C7—C8—H8B	109.8	C21—O10—K1	114.61 (15)
H8A—C8—H8B	108.3	O10—C21—C22	109.3 (2)
C9—O6—C8	112.7 (2)	O10—C21—H21A	109.8
C9—O6—K1	120.67 (15)	C22—C21—H21A	109.8
C8—O6—K1	119.31 (16)	O10—C21—H21B	109.8
O6—C9—C10	108.9 (2)	C22—C21—H21B	109.8
O6—C9—H9A	109.9	H21A—C21—H21B	108.3
C10—C9—H9A	109.9	N2—C22—C21	113.5 (2)
O6—C9—H9B	109.9	N2—C22—H22A	108.9
C10—C9—H9B	109.9	C21—C22—H22A	108.9
H9A—C9—H9B	108.3	N2—C22—H22B	108.9
N2—C10—C9	114.6 (2)	C21—C22—H22B	108.9
N2—C10—H10A	108.6	H22A—C22—H22B	107.7
C9—C10—H10A	108.6	C10—N2—C22	110.3 (2)
N2—C10—H10B	108.6	C10—N2—C16	109.9 (2)
C9—C10—H10B	108.6	C22—N2—C16	110.1 (2)
H10A—C10—H10B	107.6	C10—N2—K1	108.21 (15)
N1—C11—C12	113.0 (2)	C22—N2—K1	108.94 (16)
N1—C11—H11A	109.0	C16—N2—K1	109.33 (17)

C17—N1—C5—C6	163.4 (2)	K1—O8—C15—C16	49.7 (3)
C11—N1—C5—C6	−76.4 (3)	O8—C15—C16—N2	−63.7 (4)
K1—N1—C5—C6	42.1 (3)	C11—N1—C17—C18	161.4 (2)
N1—C5—C6—O5	−68.5 (3)	C5—N1—C17—C18	−78.5 (3)
C5—C6—O5—C7	−176.8 (2)	K1—N1—C17—C18	41.0 (3)
C5—C6—O5—K1	55.4 (3)	N1—C17—C18—O9	−65.0 (3)
C6—O5—C7—C8	178.1 (2)	C17—C18—O9—C19	−170.7 (2)
K1—O5—C7—C8	−53.7 (3)	C17—C18—O9—K1	53.5 (3)
O5—C7—C8—O6	61.3 (3)	C18—O9—C19—C20	−179.4 (2)
C7—C8—O6—C9	170.6 (2)	K1—O9—C19—C20	−44.3 (3)
C7—C8—O6—K1	−38.9 (3)	O9—C19—C20—O10	64.3 (3)
C8—O6—C9—C10	−166.3 (2)	C19—C20—O10—C21	176.4 (2)
K1—O6—C9—C10	43.8 (3)	C19—C20—O10—K1	−52.4 (3)
O6—C9—C10—N2	−61.4 (3)	C20—O10—C21—C22	−177.2 (2)
C17—N1—C11—C12	−78.8 (3)	K1—O10—C21—C22	51.4 (3)
C5—N1—C11—C12	161.2 (2)	O10—C21—C22—N2	−68.2 (3)
K1—N1—C11—C12	43.0 (3)	C9—C10—N2—C22	−72.8 (3)
N1—C11—C12—O7	−68.3 (3)	C9—C10—N2—C16	165.6 (2)
C11—C12—O7—C13	−175.0 (2)	C9—C10—N2—K1	46.3 (3)
C11—C12—O7—K1	54.9 (3)	C21—C22—N2—C10	164.9 (2)
C12—O7—C13—C14	179.8 (2)	C21—C22—N2—C16	−73.7 (3)
K1—O7—C13—C14	−49.7 (3)	C21—C22—N2—K1	46.2 (3)
O7—C13—C14—O8	67.6 (3)	C15—C16—N2—C10	−74.6 (3)
C13—C14—O8—C15	172.7 (2)	C15—C16—N2—C22	163.7 (3)
C13—C14—O8—K1	−50.5 (2)	C15—C16—N2—K1	44.1 (3)
C14—O8—C15—C16	−175.5 (2)

Selected bond lengths (Å) top

Co1—C4	1.762 (3)	Co1—C1	1.767 (3)
Co1—C3	1.763 (4)	Co1—C2	1.770 (4)

Acknowledgements

This research was supported by the US National Science Foundation and the donors of the Petroleum Research Fund, administered by the American Chemical Society.

References

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