A one-dimensional polymeric cobalt(III)-potassium complex with 18-crown-6, cyanide and porphyrinate ligands.

The reaction of Co(II)(TpivPP) {TpivPP is the dianion of 5,10,15,20-tetra-kis-[2-(2,2-di-methyl-propanamido)-phen-yl]por-ph-yrin} with an excess of KCN salts and an excess of the 18-crown-6 in chloro-benzene leads to the polymeric title compound catena-poly[[dicyanido-2κ(2) C-(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-1κ(6) O){μ3-(2α,2β)-5,10,15,20-tetra-kis-[2-(2,2-di-methyl-propanamido)-phen-yl]porphyrinato-1κO (5):2κ(4) N,N',N'',N''':1'κO (15)}cobalt(III)potassium] dihydrate], {[CoK(CN)2(C12H24O6)(C64H64N8O4]·2H2O} n . The Co(III) ion lies on an inversion center, and the asymmetric unit contains one half of a [Co(III)(2α,2β-TpivPP)(CN)2](-) ion complex and one half of a [K(18-C-6](+) counter-ion (18-C-6 is 1,4,7,10,13,16-hexa-oxa-cyclo-octa-deca-ne), where the K(I) ion lies on an inversion center. The Co(III) ion is hexa-coordinated by two C-bonded axial cyanide ligands and the four pyrrole N atoms of the porphyrin ligand. The K(I) ion is chelated by the six O atoms of the 18-crown-6 mol-ecule and is further coordinated by two O atoms of pivalamido groups of the porphyrin ligands, leading to the formation of polymeric chains running along [011]. In the crystal, the polymeric chains and the lattice water mol-ecules are linked by N-H⋯O and O-H⋯N hydrogen bonds, as well as weak C-H⋯O, O-H⋯π and C-H⋯π inter-actions into a three-dimensional supra-molecular architecture.

Related literature

For the synthesis, see: Collman et al. (1978 ▶). For related structures, see: Iimuna et al. (1988 ▶); Hoshino et al. (2000 ▶); Konarev et al. (2003 ▶); Ali et al. (2011 ▶); Pratt (1972 ▶); Li et al. (2010 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[CoK(CN)2(C12H24O6)(C64H64N8O4]·2H2O

M = 1459.70

Triclinic,

a = 9.1885 (3) Å

b = 14.4631 (4) Å

c = 14.6845 (4) Å

α = 98.342 (2)°

β = 102.170 (2)°

γ = 93.101 (2)°

V = 1880.20 (10) Å3

Z = 1

Mo Kα radiation

μ = 0.35 mm−1

T = 180 K

0.48 × 0.40 × 0.30 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.86, T max = 0.90

38025 measured reflections

7400 independent reflections

5986 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.105

S = 1.07

7400 reflections

475 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.38 e Å−3

Δρmin = −0.26 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814003596/xu5770sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003596/xu5770Isup2.hkl

CCDC reference: 987431

Additional supporting information: crystallographic information; 3D view; checkCIF report

[CoK(CN)2(C12H24O6)(C64H64N8O4]·2H2O	Z = 1
Mr = 1459.70	F(000) = 772
Triclinic, P1	Dx = 1.289 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1885 (3) Å	Cell parameters from 7400 reflections
b = 14.4631 (4) Å	θ = 2.9–26.1°
c = 14.6845 (4) Å	µ = 0.35 mm−1
α = 98.342 (2)°	T = 180 K
β = 102.170 (2)°	Prism, dark purple
γ = 93.101 (2)°	0.48 × 0.40 × 0.30 mm
V = 1880.20 (10) Å3

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	7400 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5986 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 16.1978 pixels mm-1	θmax = 26.0°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −17→17
Tmin = 0.86, Tmax = 0.90	l = −18→18
38025 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0598P)2 + 0.4188P] where P = (Fo2 + 2Fc2)/3
7400 reflections	(Δ/σ)max = 0.001
475 parameters	Δρmax = 0.38 e Å−3
2 restraints	Δρmin = −0.26 e Å−3

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

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Co	0.5000	1.0000	1.0000	0.02133 (10)
N1	0.52932 (15)	0.88932 (9)	1.06541 (9)	0.0234 (3)
N2	0.39217 (15)	0.91778 (9)	0.88238 (10)	0.0241 (3)
N3	0.94155 (17)	0.88392 (11)	1.27847 (11)	0.0329 (3)
HN3	0.9590	0.9249	1.2424	0.039*
N4	0.57697 (19)	0.65256 (12)	0.83577 (12)	0.0397 (4)
HN4	0.6294	0.6952	0.8815	0.048*
N5	0.7928 (2)	0.97203 (13)	0.93683 (14)	0.0464 (4)
O1	0.97516 (19)	0.73834 (11)	1.31093 (12)	0.0533 (4)
O2	0.5711 (2)	0.57652 (13)	0.69039 (11)	0.0646 (5)
C1	0.66304 (19)	0.96624 (12)	1.22370 (12)	0.0265 (4)
C2	0.60058 (19)	0.88825 (12)	1.15701 (12)	0.0252 (4)
C3	0.6008 (2)	0.79372 (13)	1.17555 (13)	0.0316 (4)
H3	0.6432	0.7742	1.2337	0.038*
C4	0.5306 (2)	0.73807 (12)	1.09608 (13)	0.0315 (4)
H4	0.5144	0.6716	1.0869	0.038*
C5	0.48427 (19)	0.79756 (12)	1.02721 (12)	0.0253 (4)
C6	0.40387 (19)	0.76506 (12)	0.93650 (12)	0.0262 (4)
C7	0.36008 (19)	0.82279 (12)	0.87009 (12)	0.0264 (4)
C8	0.2772 (2)	0.78898 (13)	0.77591 (13)	0.0330 (4)
H8	0.2400	0.7259	0.7503	0.040*
C9	0.2623 (2)	0.86297 (13)	0.73112 (13)	0.0331 (4)
H9	0.2128	0.8623	0.6673	0.040*
C10	0.33430 (19)	0.94339 (12)	0.79678 (12)	0.0260 (4)
C11	0.7262 (2)	0.95246 (12)	1.32261 (12)	0.0303 (4)
C12	0.6505 (2)	0.98329 (15)	1.39281 (14)	0.0403 (5)
H12	0.5619	1.0140	1.3770	0.048*
C13	0.7022 (3)	0.96996 (16)	1.48480 (15)	0.0467 (5)
H13	0.6494	0.9909	1.5319	0.056*
C14	0.8304 (3)	0.92624 (16)	1.50768 (14)	0.0470 (5)
H14	0.8657	0.9165	1.5709	0.056*
C15	0.9088 (2)	0.89617 (14)	1.43992 (14)	0.0394 (5)
H15	0.9978	0.8661	1.4566	0.047*
C16	0.8571 (2)	0.91008 (13)	1.34684 (13)	0.0310 (4)
C17	0.9971 (2)	0.79926 (14)	1.26544 (14)	0.0355 (4)
C18	1.0893 (2)	0.78598 (16)	1.18982 (14)	0.0421 (5)
C19	1.1415 (3)	0.68749 (19)	1.18373 (18)	0.0592 (7)
H19A	1.2030	0.6799	1.2449	0.089*
H19B	1.2006	0.6780	1.1354	0.089*
H19C	1.0544	0.6412	1.1670	0.089*
C20	0.9932 (3)	0.7967 (2)	1.09392 (16)	0.0614 (7)
H20A	0.9085	0.7486	1.0764	0.092*
H20B	1.0536	0.7892	1.0461	0.092*
H20C	0.9560	0.8590	1.0978	0.092*
C21	1.2242 (3)	0.85800 (19)	1.21753 (18)	0.0542 (6)
H21A	1.1904	0.9213	1.2210	0.081*
H21B	1.2852	0.8487	1.1702	0.081*
H21C	1.2839	0.8504	1.2793	0.081*
C22	0.3639 (2)	0.66159 (12)	0.90657 (12)	0.0291 (4)
C23	0.2404 (2)	0.61838 (14)	0.92750 (16)	0.0428 (5)
H23	0.1823	0.6543	0.9634	0.051*
C24	0.1995 (3)	0.52378 (15)	0.89726 (17)	0.0509 (6)
H24	0.1138	0.4950	0.9120	0.061*
C25	0.2836 (3)	0.47170 (14)	0.84571 (16)	0.0467 (5)
H25	0.2553	0.4067	0.8243	0.056*
C26	0.4078 (3)	0.51240 (14)	0.82480 (14)	0.0419 (5)
H26	0.4662	0.4755	0.7898	0.050*
C27	0.4487 (2)	0.60767 (13)	0.85471 (13)	0.0319 (4)
C28	0.6291 (2)	0.63779 (15)	0.75535 (14)	0.0403 (5)
C29	0.7599 (2)	0.70560 (17)	0.75141 (15)	0.0457 (5)
C30	0.8447 (3)	0.6566 (2)	0.6829 (2)	0.0762 (9)
H30A	0.8931	0.6047	0.7094	0.114*
H30B	0.9209	0.7014	0.6722	0.114*
H30C	0.7750	0.6321	0.6228	0.114*
C31	0.6936 (3)	0.79227 (19)	0.71477 (19)	0.0628 (7)
H31A	0.6252	0.7727	0.6531	0.094*
H31B	0.7745	0.8362	0.7084	0.094*
H31C	0.6389	0.8231	0.7595	0.094*
C32	0.8650 (3)	0.73621 (19)	0.84737 (17)	0.0562 (6)
H32A	0.8144	0.7761	0.8885	0.084*
H32B	0.9545	0.7715	0.8397	0.084*
H32C	0.8938	0.6807	0.8757	0.084*
C33	0.6838 (2)	0.98363 (12)	0.96064 (12)	0.0290 (4)
K	0.5000	0.5000	0.5000	0.03158 (14)
O3	0.22357 (15)	0.57249 (10)	0.52236 (9)	0.0391 (3)
O4	0.45230 (16)	0.68329 (10)	0.47014 (10)	0.0403 (3)
O5	0.68531 (15)	0.59387 (9)	0.41262 (10)	0.0381 (3)
C34	0.8311 (2)	0.56578 (16)	0.41702 (15)	0.0428 (5)
H34A	0.8960	0.5911	0.4795	0.051*
H34B	0.8744	0.5901	0.3680	0.051*
C35	0.1781 (2)	0.53796 (16)	0.59851 (15)	0.0436 (5)
H35A	0.0793	0.5594	0.6039	0.052*
H35B	0.2507	0.5630	0.6582	0.052*
C36	0.2412 (3)	0.67115 (15)	0.53654 (16)	0.0464 (5)
H36A	0.3102	0.6946	0.5981	0.056*
H36B	0.1434	0.6963	0.5378	0.056*
C37	0.3018 (3)	0.70415 (16)	0.45976 (17)	0.0497 (5)
H37A	0.2425	0.6726	0.3977	0.060*
H37B	0.2957	0.7726	0.4630	0.060*
C38	0.5214 (3)	0.71294 (16)	0.40086 (16)	0.0470 (5)
H38A	0.5153	0.7812	0.4018	0.056*
H38B	0.4691	0.6800	0.3376	0.056*
C39	0.6799 (2)	0.69204 (14)	0.42005 (16)	0.0445 (5)
H39A	0.7307	0.7161	0.3740	0.053*
H39B	0.7316	0.7230	0.4842	0.053*
O6	0.97562 (19)	1.03103 (13)	1.16135 (13)	0.0560 (4)
H1O6	1.053 (2)	1.032 (2)	1.136 (2)	0.084*
H2O6	0.890 (2)	1.038 (2)	1.1234 (17)	0.084*

	U11	U22	U33	U12	U13	U23
Co	0.02503 (18)	0.01677 (16)	0.02392 (17)	0.00123 (12)	0.00987 (13)	0.00257 (12)
N1	0.0261 (7)	0.0199 (7)	0.0256 (7)	0.0015 (5)	0.0096 (6)	0.0030 (6)
N2	0.0294 (8)	0.0185 (7)	0.0268 (7)	0.0021 (6)	0.0119 (6)	0.0031 (6)
N3	0.0344 (9)	0.0331 (8)	0.0345 (8)	0.0009 (7)	0.0114 (7)	0.0117 (7)
N4	0.0441 (10)	0.0353 (9)	0.0378 (9)	−0.0003 (7)	0.0152 (8)	−0.0081 (7)
N5	0.0391 (10)	0.0504 (11)	0.0590 (11)	0.0087 (8)	0.0280 (9)	0.0125 (9)
O1	0.0638 (10)	0.0423 (9)	0.0683 (10)	0.0127 (8)	0.0343 (9)	0.0243 (8)
O2	0.0722 (12)	0.0741 (12)	0.0382 (9)	−0.0237 (9)	0.0190 (8)	−0.0202 (8)
C1	0.0288 (9)	0.0280 (9)	0.0253 (8)	0.0022 (7)	0.0111 (7)	0.0055 (7)
C2	0.0261 (9)	0.0244 (8)	0.0280 (9)	0.0014 (7)	0.0112 (7)	0.0059 (7)
C3	0.0366 (10)	0.0274 (9)	0.0324 (9)	0.0006 (8)	0.0077 (8)	0.0107 (7)
C4	0.0380 (10)	0.0218 (9)	0.0354 (10)	0.0017 (7)	0.0082 (8)	0.0071 (7)
C5	0.0288 (9)	0.0200 (8)	0.0294 (9)	0.0029 (7)	0.0111 (7)	0.0044 (7)
C6	0.0304 (9)	0.0201 (8)	0.0307 (9)	0.0030 (7)	0.0131 (7)	0.0028 (7)
C7	0.0301 (9)	0.0214 (8)	0.0288 (9)	0.0015 (7)	0.0109 (7)	0.0017 (7)
C8	0.0440 (11)	0.0220 (9)	0.0308 (9)	−0.0001 (8)	0.0081 (8)	−0.0018 (7)
C9	0.0422 (11)	0.0287 (9)	0.0271 (9)	0.0019 (8)	0.0073 (8)	0.0010 (7)
C10	0.0294 (9)	0.0242 (9)	0.0261 (9)	0.0021 (7)	0.0115 (7)	0.0018 (7)
C11	0.0380 (10)	0.0261 (9)	0.0274 (9)	−0.0046 (7)	0.0099 (8)	0.0046 (7)
C12	0.0479 (12)	0.0417 (11)	0.0342 (10)	0.0005 (9)	0.0169 (9)	0.0055 (9)
C13	0.0596 (14)	0.0496 (13)	0.0332 (11)	−0.0040 (11)	0.0203 (10)	0.0030 (9)
C14	0.0638 (15)	0.0462 (12)	0.0282 (10)	−0.0153 (11)	0.0082 (10)	0.0069 (9)
C15	0.0446 (12)	0.0362 (11)	0.0346 (10)	−0.0079 (9)	0.0027 (9)	0.0096 (8)
C16	0.0364 (10)	0.0272 (9)	0.0288 (9)	−0.0074 (7)	0.0074 (8)	0.0057 (7)
C17	0.0294 (10)	0.0406 (11)	0.0372 (10)	0.0011 (8)	0.0064 (8)	0.0112 (9)
C18	0.0416 (12)	0.0512 (13)	0.0376 (11)	0.0113 (10)	0.0129 (9)	0.0119 (9)
C19	0.0670 (16)	0.0624 (16)	0.0539 (14)	0.0226 (13)	0.0226 (13)	0.0087 (12)
C20	0.0686 (17)	0.0807 (19)	0.0368 (12)	0.0225 (14)	0.0115 (11)	0.0100 (12)
C21	0.0397 (12)	0.0689 (16)	0.0620 (15)	0.0056 (11)	0.0215 (11)	0.0215 (12)
C22	0.0377 (10)	0.0211 (9)	0.0274 (9)	0.0016 (7)	0.0059 (8)	0.0032 (7)
C23	0.0487 (12)	0.0308 (10)	0.0512 (12)	−0.0017 (9)	0.0213 (10)	0.0006 (9)
C24	0.0595 (14)	0.0321 (11)	0.0621 (15)	−0.0131 (10)	0.0230 (12)	0.0027 (10)
C25	0.0666 (15)	0.0200 (9)	0.0500 (13)	−0.0018 (9)	0.0085 (11)	0.0030 (9)
C26	0.0586 (13)	0.0252 (10)	0.0413 (11)	0.0085 (9)	0.0116 (10)	0.0006 (8)
C27	0.0399 (10)	0.0247 (9)	0.0303 (9)	0.0043 (8)	0.0071 (8)	0.0022 (7)
C28	0.0408 (11)	0.0446 (12)	0.0332 (10)	0.0065 (9)	0.0081 (9)	−0.0021 (9)
C29	0.0418 (12)	0.0561 (14)	0.0371 (11)	−0.0009 (10)	0.0137 (9)	−0.0054 (10)
C30	0.0638 (17)	0.092 (2)	0.0712 (18)	−0.0076 (15)	0.0391 (15)	−0.0223 (16)
C31	0.0665 (17)	0.0651 (17)	0.0558 (15)	−0.0081 (13)	0.0110 (13)	0.0149 (13)
C32	0.0459 (13)	0.0666 (16)	0.0499 (14)	−0.0052 (11)	0.0062 (11)	−0.0014 (12)
C33	0.0339 (10)	0.0238 (9)	0.0307 (9)	0.0018 (7)	0.0105 (8)	0.0046 (7)
K	0.0369 (3)	0.0262 (3)	0.0338 (3)	−0.0001 (2)	0.0138 (2)	0.0039 (2)
O3	0.0444 (8)	0.0407 (8)	0.0360 (7)	0.0079 (6)	0.0158 (6)	0.0073 (6)
O4	0.0450 (8)	0.0373 (8)	0.0433 (8)	0.0077 (6)	0.0140 (6)	0.0143 (6)
O5	0.0345 (7)	0.0349 (7)	0.0473 (8)	−0.0021 (6)	0.0142 (6)	0.0086 (6)
C34	0.0333 (11)	0.0562 (13)	0.0420 (11)	0.0004 (9)	0.0112 (9)	0.0149 (10)
C35	0.0399 (11)	0.0586 (14)	0.0377 (11)	0.0109 (10)	0.0169 (9)	0.0104 (10)
C36	0.0466 (12)	0.0400 (12)	0.0550 (13)	0.0098 (10)	0.0181 (10)	0.0029 (10)
C37	0.0508 (13)	0.0432 (12)	0.0599 (14)	0.0148 (10)	0.0138 (11)	0.0182 (11)
C38	0.0568 (14)	0.0400 (12)	0.0509 (13)	0.0039 (10)	0.0171 (11)	0.0220 (10)
C39	0.0504 (13)	0.0358 (11)	0.0506 (13)	−0.0068 (9)	0.0144 (10)	0.0170 (9)
O6	0.0493 (10)	0.0643 (11)	0.0697 (12)	0.0116 (8)	0.0359 (9)	0.0250 (9)

Co—N1	1.9853 (13)	C21—H21A	0.9800
Co—N1i	1.9853 (13)	C21—H21B	0.9800
Co—N2	1.9834 (14)	C21—H21C	0.9800
Co—N2i	1.9834 (14)	C22—C23	1.378 (3)
Co—C33	1.9129 (18)	C22—C27	1.392 (2)
Co—C33i	1.9129 (18)	C23—C24	1.381 (3)
N1—C5	1.369 (2)	C23—H23	0.9500
N1—C2	1.369 (2)	C24—C25	1.372 (3)
N2—C7	1.367 (2)	C24—H24	0.9500
N2—C10	1.369 (2)	C25—C26	1.368 (3)
N3—C17	1.355 (2)	C25—H25	0.9500
N3—C16	1.416 (2)	C26—C27	1.390 (3)
N3—HN3	0.8800	C26—H26	0.9500
N4—C28	1.359 (2)	C28—C29	1.526 (3)
N4—C27	1.413 (3)	C29—C30	1.519 (3)
N4—HN4	0.8800	C29—C32	1.521 (3)
N5—C33	1.141 (2)	C29—C31	1.540 (4)
O1—C17	1.213 (2)	C30—H30A	0.9800
O2—C28	1.212 (3)	C30—H30B	0.9800
O2—K	2.7789 (15)	C30—H30C	0.9800
C1—C10i	1.383 (2)	C31—H31A	0.9800
C1—C2	1.390 (2)	C31—H31B	0.9800
C1—C11	1.492 (2)	C31—H31C	0.9800
C2—C3	1.432 (2)	C32—H32A	0.9800
C3—C4	1.334 (3)	C32—H32B	0.9800
C3—H3	0.9500	C32—H32C	0.9800
C4—C5	1.433 (2)	K—O2ii	2.7789 (15)
C4—H4	0.9500	K—O3ii	2.8633 (13)
C5—C6	1.381 (2)	K—O3	2.8633 (13)
C6—C7	1.385 (2)	K—O4ii	2.7917 (13)
C6—C22	1.500 (2)	K—O4	2.7917 (13)
C7—C8	1.432 (3)	K—O5ii	2.7505 (13)
C8—C9	1.334 (3)	K—O5	2.7505 (13)
C8—H8	0.9500	O3—C36	1.407 (3)
C9—C10	1.429 (3)	O3—C35	1.418 (2)
C9—H9	0.9500	O4—C38	1.411 (2)
C10—C1i	1.383 (2)	O4—C37	1.413 (3)
C11—C16	1.383 (3)	O5—C34	1.412 (2)
C11—C12	1.395 (3)	O5—C39	1.412 (2)
C12—C13	1.379 (3)	C34—C35ii	1.480 (3)
C12—H12	0.9500	C34—H34A	0.9900
C13—C14	1.369 (3)	C34—H34B	0.9900
C13—H13	0.9500	C35—C34ii	1.480 (3)
C14—C15	1.382 (3)	C35—H35A	0.9900
C14—H14	0.9500	C35—H35B	0.9900
C15—C16	1.397 (3)	C36—C37	1.484 (3)
C15—H15	0.9500	C36—H36A	0.9900
C17—C18	1.530 (3)	C36—H36B	0.9900
C18—C21	1.520 (3)	C37—H37A	0.9900
C18—C19	1.524 (3)	C37—H37B	0.9900
C18—C20	1.530 (3)	C38—C39	1.480 (3)
C19—H19A	0.9800	C38—H38A	0.9900
C19—H19B	0.9800	C38—H38B	0.9900
C19—H19C	0.9800	C39—H39A	0.9900
C20—H20A	0.9800	C39—H39B	0.9900
C20—H20B	0.9800	O6—H1O6	0.869 (10)
C20—H20C	0.9800	O6—H2O6	0.881 (10)
C33—Co—C33i	180.000 (1)	C26—C25—C24	120.64 (19)
C33—Co—N2	89.44 (7)	C26—C25—H25	119.7
C33i—Co—N2	90.56 (7)	C24—C25—H25	119.7
C33—Co—N2i	90.56 (7)	C25—C26—C27	119.98 (19)
C33i—Co—N2i	89.44 (7)	C25—C26—H26	120.0
N2—Co—N2i	180.000 (1)	C27—C26—H26	120.0
C33—Co—N1	89.73 (6)	C26—C27—C22	120.04 (18)
C33i—Co—N1	90.27 (7)	C26—C27—N4	122.02 (17)
N2—Co—N1	90.40 (6)	C22—C27—N4	117.93 (16)
N2i—Co—N1	89.60 (6)	O2—C28—N4	121.5 (2)
C33—Co—N1i	90.27 (7)	O2—C28—C29	122.94 (19)
C33i—Co—N1i	89.73 (6)	N4—C28—C29	115.55 (17)
N2—Co—N1i	89.60 (6)	C30—C29—C32	109.7 (2)
N2i—Co—N1i	90.40 (6)	C30—C29—C28	107.74 (19)
N1—Co—N1i	180.000 (1)	C32—C29—C28	112.59 (19)
C5—N1—C2	105.66 (14)	C30—C29—C31	110.3 (2)
C5—N1—Co	126.80 (11)	C32—C29—C31	109.3 (2)
C2—N1—Co	127.53 (11)	C28—C29—C31	107.20 (18)
C7—N2—C10	105.43 (14)	C29—C30—H30A	109.5
C7—N2—Co	126.81 (12)	C29—C30—H30B	109.5
C10—N2—Co	127.76 (11)	H30A—C30—H30B	109.5
C17—N3—C16	123.67 (16)	C29—C30—H30C	109.5
C17—N3—HN3	118.2	H30A—C30—H30C	109.5
C16—N3—HN3	118.2	H30B—C30—H30C	109.5
C28—N4—C27	127.75 (17)	C29—C31—H31A	109.5
C28—N4—HN4	116.1	C29—C31—H31B	109.5
C27—N4—HN4	116.1	H31A—C31—H31B	109.5
C28—O2—K	152.04 (16)	C29—C31—H31C	109.5
C10i—C1—C2	122.97 (16)	H31A—C31—H31C	109.5
C10i—C1—C11	118.31 (15)	H31B—C31—H31C	109.5
C2—C1—C11	118.70 (15)	C29—C32—H32A	109.5
N1—C2—C1	126.06 (15)	C29—C32—H32B	109.5
N1—C2—C3	109.87 (15)	H32A—C32—H32B	109.5
C1—C2—C3	124.07 (16)	C29—C32—H32C	109.5
C4—C3—C2	107.40 (16)	H32A—C32—H32C	109.5
C4—C3—H3	126.3	H32B—C32—H32C	109.5
C2—C3—H3	126.3	N5—C33—Co	178.67 (17)
C3—C4—C5	107.01 (16)	O5ii—K—O5	180.0
C3—C4—H4	126.5	O5ii—K—O2	72.53 (5)
C5—C4—H4	126.5	O5—K—O2	107.47 (5)
N1—C5—C6	126.14 (15)	O5ii—K—O2ii	107.47 (5)
N1—C5—C4	110.06 (15)	O5—K—O2ii	72.53 (5)
C6—C5—C4	123.80 (16)	O2—K—O2ii	180.000 (1)
C5—C6—C7	123.56 (16)	O5ii—K—O4ii	60.15 (4)
C5—C6—C22	118.87 (15)	O5—K—O4ii	119.85 (4)
C7—C6—C22	117.55 (16)	O2—K—O4ii	94.94 (5)
N2—C7—C6	126.18 (16)	O2ii—K—O4ii	85.06 (5)
N2—C7—C8	110.27 (15)	O5ii—K—O4	119.85 (4)
C6—C7—C8	123.51 (16)	O5—K—O4	60.15 (4)
C9—C8—C7	106.85 (16)	O2—K—O4	85.06 (5)
C9—C8—H8	126.6	O2ii—K—O4	94.94 (5)
C7—C8—H8	126.6	O4ii—K—O4	180.0
C8—C9—C10	107.43 (16)	O5ii—K—O3ii	119.74 (4)
C8—C9—H9	126.3	O5—K—O3ii	60.26 (4)
C10—C9—H9	126.3	O2—K—O3ii	100.93 (5)
N2—C10—C1i	126.01 (16)	O2ii—K—O3ii	79.07 (5)
N2—C10—C9	110.00 (15)	O4ii—K—O3ii	61.01 (4)
C1i—C10—C9	123.91 (16)	O4—K—O3ii	118.99 (4)
C16—C11—C12	119.00 (17)	O5ii—K—O3	60.26 (4)
C16—C11—C1	122.11 (16)	O5—K—O3	119.74 (4)
C12—C11—C1	118.89 (17)	O2—K—O3	79.07 (5)
C13—C12—C11	121.1 (2)	O2ii—K—O3	100.93 (5)
C13—C12—H12	119.5	O4ii—K—O3	118.99 (4)
C11—C12—H12	119.5	O4—K—O3	61.01 (4)
C14—C13—C12	119.4 (2)	O3ii—K—O3	180.00 (5)
C14—C13—H13	120.3	C36—O3—C35	111.99 (15)
C12—C13—H13	120.3	C36—O3—K	109.43 (12)
C13—C14—C15	120.76 (19)	C35—O3—K	109.30 (11)
C13—C14—H14	119.6	C38—O4—C37	113.48 (16)
C15—C14—H14	119.6	C38—O4—K	114.07 (11)
C14—C15—C16	119.9 (2)	C37—O4—K	114.16 (12)
C14—C15—H15	120.1	C34—O5—C39	112.95 (16)
C16—C15—H15	120.1	C34—O5—K	118.22 (11)
C11—C16—C15	119.81 (17)	C39—O5—K	117.03 (11)
C11—C16—N3	120.22 (16)	O5—C34—C35ii	108.25 (17)
C15—C16—N3	119.93 (18)	O5—C34—H34A	110.0
O1—C17—N3	122.09 (18)	C35ii—C34—H34A	110.0
O1—C17—C18	122.41 (18)	O5—C34—H34B	110.0
N3—C17—C18	115.49 (17)	C35ii—C34—H34B	110.0
C21—C18—C19	109.60 (19)	H34A—C34—H34B	108.4
C21—C18—C17	109.07 (18)	O3—C35—C34ii	110.08 (16)
C19—C18—C17	108.66 (18)	O3—C35—H35A	109.6
C21—C18—C20	110.6 (2)	C34ii—C35—H35A	109.6
C19—C18—C20	108.8 (2)	O3—C35—H35B	109.6
C17—C18—C20	110.01 (17)	C34ii—C35—H35B	109.6
C18—C19—H19A	109.5	H35A—C35—H35B	108.2
C18—C19—H19B	109.5	O3—C36—C37	110.25 (17)
H19A—C19—H19B	109.5	O3—C36—H36A	109.6
C18—C19—H19C	109.5	C37—C36—H36A	109.6
H19A—C19—H19C	109.5	O3—C36—H36B	109.6
H19B—C19—H19C	109.5	C37—C36—H36B	109.6
C18—C20—H20A	109.5	H36A—C36—H36B	108.1
C18—C20—H20B	109.5	O4—C37—C36	108.89 (18)
H20A—C20—H20B	109.5	O4—C37—H37A	109.9
C18—C20—H20C	109.5	C36—C37—H37A	109.9
H20A—C20—H20C	109.5	O4—C37—H37B	109.9
H20B—C20—H20C	109.5	C36—C37—H37B	109.9
C18—C21—H21A	109.5	H37A—C37—H37B	108.3
C18—C21—H21B	109.5	O4—C38—C39	109.51 (17)
H21A—C21—H21B	109.5	O4—C38—H38A	109.8
C18—C21—H21C	109.5	C39—C38—H38A	109.8
H21A—C21—H21C	109.5	O4—C38—H38B	109.8
H21B—C21—H21C	109.5	C39—C38—H38B	109.8
C23—C22—C27	118.63 (17)	H38A—C38—H38B	108.2
C23—C22—C6	120.80 (16)	O5—C39—C38	108.63 (17)
C27—C22—C6	120.55 (16)	O5—C39—H39A	110.0
C22—C23—C24	121.24 (19)	C38—C39—H39A	110.0
C22—C23—H23	119.4	O5—C39—H39B	110.0
C24—C23—H23	119.4	C38—C39—H39B	110.0
C25—C24—C23	119.5 (2)	H39A—C39—H39B	108.3
C25—C24—H24	120.3	H1O6—O6—H2O6	115 (3)
C23—C24—H24	120.3

D—H···A	D—H	H···A	D···A	D—H···A
N3—HN3···O6	0.88	2.09	2.966 (2)	172
O6—H1O6···N5iii	0.87	1.95 (2)	2.810 (3)	172 (2)
C20—H20C···O6	0.98	2.51	3.413 (3)	153
O6—H2O6···Cg2i	0.88	2.73 (2)	3.272 (2)	121 (2)
O6—H2O6···Cg3	0.88	2.81 (2)	3.455 (2)	131 (2)
O6—H2O6···Cg5i	0.88	2.81 (2)	3.455 (2)	131 (2)
C21—H21B···Cg1iv	0.98	2.82	3.737 (3)	156

Table 1

Selected bond lengths (Å)

Co—N1	1.9853 (13)
Co—N2	1.9834 (14)
Co—C33	1.9129 (18)
K—O2i	2.7789 (15)
K—O3	2.8633 (13)
K—O4	2.7917 (13)
K—O5	2.7505 (13)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg3 and Cg5 are the centroids of the N1/C2–C5, N2/C7–C10, Co/N1/C2/C1/C10′/N2′ and Co/N2/C10/C1′/C2′/N1′ rings respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—HN3⋯O6	0.88	2.09	2.966 (2)	172
O6—H1O6⋯N5ii	0.87	1.95 (2)	2.810 (3)	172 (2)
C20—H20C⋯O6	0.98	2.51	3.413 (3)	153
O6—H2O6⋯Cg2iii	0.88	2.73 (2)	3.272 (2)	121 (2)
O6—H2O6⋯Cg3	0.88	2.81 (2)	3.455 (2)	131 (2)
O6—H2O6⋯Cg5iii	0.88	2.81 (2)	3.455 (2)	131 (2)
C21—H21B⋯Cg1iv	0.98	2.82	3.737 (3)	156

Symmetry codes: (ii) ; (iii) ; (iv) .