Chlorido(pyridine-κN)(5,10,15,20-tetra-phenyl-porphyrinato-κ(4)N)cobalt(III) chloro-form hemisolvate.

In the title complex, [CoCl(C(44)H(28)N(4))(C(5)H(5)N)]·0.5CHCl(3) or [Co(III)(TPP)Cl(py)]·0.5CHCl(3) (where TPP is the dianion of tetra-phenyl-porphyrin and py is pyridine), the average equatorial cobalt-pyrrole N atom bond length (Co-N(p)) is 1.958 (7) Å and the axial Co-Cl and Co-N(py) distances are 2.2339 (6) and 1.9898 (17) Å, respectively. The tetra-phenyl-porphyrinate dianion exhibits an important nonplanar conformation with major ruffling and saddling distortions. In the crystal, mol-ecules are linked via weak C-H⋯π inter-actions. In the difference Fourier map, a region of highly disordered electron density was estimated using the SQUEEZE routine [PLATON; Spek (2009 ▶), Acta Cryst. D65, 148-155] to be equivalent to one half-mol-ecule of CHCl(3) per mol-ecule of the complex.

Related literature

For general background on cobalt porphyrin species and their applications, see: Sanders et al. (2000 ▶). For the synthesis of Co(II) tetra­phenyl­porphyrin, see: Madure & Scheidt (1976 ▶). For metalloporphyrins used as biomimetic models for haemoproteines, see: Dhifet et al. (2010 ▶); Mansour et al. (2010 ▶). For the structures of related compounds, see: Ali et al. (2011 ▶); Goodwin et al. (2001 ▶); Hodgson et al. (2002 ▶); Iimuna et al. (1988 ▶); Jentzen et al. (1997 ▶); Konarev et al. (2003 ▶); Mikolaiski et al. (1989 ▶); Sakurai et al. (1976 ▶); Shirazi & Goff (1982 ▶); Toronto et al. (1998 ▶). For the Cambridge Structural Database, see: Allen (2002 ▶). For details of the SQUEEZE routine in PLATON, see: Spek (2009 ▶).

Experimental

Crystal data

[CoCl(C44H28N4)(C5H5N)]·0.5CHCl3

M = 845.90

Monoclinic,

a = 13.0467 (3) Å

b = 23.4240 (7) Å

c = 14.3264 (5) Å

β = 103.541 (3)°

V = 4256.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.60 mm−1

T = 180 K

0.45 × 0.37 × 0.36 mm

Data collection

Oxford Xcalibur Sapphire2 diffractometer with a large Be window

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.802, T max = 0.804

43618 measured reflections

8690 independent reflections

7213 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.108

S = 1.07

8690 reflections

505 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032564/su2453sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032564/su2453Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CoCl(C44H28N4)(C5H5N)]·0.5CHCl3	F(000) = 1740
Mr = 845.90	Dx = 1.315 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25194 reflections
a = 13.0467 (3) Å	θ = 3.0–26.4°
b = 23.4240 (7) Å	µ = 0.60 mm−1
c = 14.3264 (5) Å	T = 180 K
β = 103.541 (3)°	Prism, dark purple
V = 4256.5 (2) Å3	0.45 × 0.37 × 0.36 mm
Z = 4

Oxford Xcalibur Sapphire2 diffractometer with a large Be window	8690 independent reflections
Radiation source: fine-focus sealed tube	7213 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 8.2632 pixels mm-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −29→29
Tmin = 0.802, Tmax = 0.804	l = −17→17
43618 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0587P)2 + 2.0185P] where P = (Fo2 + 2Fc2)/3
8690 reflections	(Δ/σ)max = 0.001
505 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Experimental. Absorption correction: Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (CrysAlisPro; Agilent, 2010).

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 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.

	x	y	z	Uiso*/Ueq
Co	0.653649 (18)	0.198422 (10)	0.876228 (18)	0.01771 (8)
Cl	0.57928 (4)	0.13891 (2)	0.75784 (4)	0.02806 (12)
N1	0.56392 (12)	0.26163 (7)	0.81419 (12)	0.0223 (3)
N2	0.54701 (12)	0.17807 (7)	0.94669 (11)	0.0206 (3)
N3	0.74480 (11)	0.13656 (7)	0.93931 (11)	0.0190 (3)
N4	0.75900 (12)	0.21811 (7)	0.80496 (12)	0.0210 (3)
N5	0.72264 (13)	0.25204 (7)	0.97968 (12)	0.0235 (3)
C1	0.59560 (15)	0.30730 (8)	0.76759 (15)	0.0249 (4)
C2	0.51268 (16)	0.34851 (9)	0.74310 (17)	0.0335 (5)
H2	0.5156	0.3841	0.7121	0.040*
C3	0.42995 (17)	0.32728 (9)	0.77237 (18)	0.0352 (5)
H3	0.3625	0.3446	0.7640	0.042*
C4	0.46209 (15)	0.27343 (9)	0.81880 (15)	0.0261 (4)
C5	0.40233 (15)	0.24155 (9)	0.86779 (16)	0.0272 (4)
C6	0.44397 (15)	0.19627 (8)	0.92754 (15)	0.0233 (4)
C7	0.38706 (15)	0.16393 (9)	0.98388 (15)	0.0270 (4)
H7	0.3140	0.1670	0.9819	0.032*
C8	0.45596 (15)	0.12847 (9)	1.03985 (15)	0.0252 (4)
H8	0.4414	0.1028	1.0865	0.030*
C10	0.64470 (14)	0.10443 (8)	1.05469 (13)	0.0205 (4)
C11	0.73416 (14)	0.10587 (8)	1.01807 (13)	0.0198 (4)
C12	0.82315 (15)	0.06912 (8)	1.04972 (14)	0.0228 (4)
H12	0.8363	0.0451	1.1047	0.027*
C13	0.88449 (15)	0.07503 (8)	0.98695 (14)	0.0230 (4)
H13	0.9485	0.0554	0.9884	0.028*
C14	0.83511 (14)	0.11654 (8)	0.91746 (14)	0.0203 (4)
C15	0.87563 (14)	0.13505 (8)	0.84102 (14)	0.0229 (4)
C16	0.83825 (14)	0.18342 (9)	0.78865 (15)	0.0238 (4)
C17	0.88598 (16)	0.20959 (10)	0.71885 (16)	0.0320 (5)
H17	0.9389	0.1934	0.6914	0.038*
C18	0.84160 (16)	0.26142 (10)	0.69963 (16)	0.0320 (5)
H18	0.8603	0.2897	0.6590	0.038*
C19	0.76113 (15)	0.26602 (9)	0.75165 (15)	0.0249 (4)
C20	0.69111 (16)	0.31156 (9)	0.74164 (15)	0.0264 (4)
C21	0.72025 (15)	0.36591 (9)	0.70021 (17)	0.0297 (5)
C22	0.67501 (19)	0.38346 (10)	0.60764 (17)	0.0353 (5)
H22	0.6233	0.3603	0.5672	0.042*
C23	0.7047 (2)	0.43488 (10)	0.57344 (19)	0.0410 (6)
H23	0.6728	0.4468	0.5099	0.049*
C24	0.77946 (19)	0.46849 (10)	0.6304 (2)	0.0428 (6)
H24	0.7990	0.5038	0.6070	0.051*
C25	0.8261 (2)	0.45096 (12)	0.7216 (2)	0.0551 (8)
H25	0.8788	0.4739	0.7613	0.066*
C26	0.7966 (2)	0.39973 (12)	0.7561 (2)	0.0492 (7)
H26	0.8298	0.3878	0.8193	0.059*
C27	0.29171 (16)	0.25999 (9)	0.86365 (18)	0.0333 (5)
C28	0.21741 (17)	0.26194 (10)	0.7771 (2)	0.0399 (6)
H28	0.2367	0.2512	0.7196	0.048*
C29	0.11497 (19)	0.27942 (11)	0.7738 (2)	0.0525 (8)
H29	0.0647	0.2809	0.7140	0.063*
C30	0.0864 (2)	0.29440 (12)	0.8556 (3)	0.0603 (9)
H30	0.0159	0.3059	0.8529	0.072*
C31	0.1585 (2)	0.29308 (13)	0.9420 (3)	0.0613 (9)
H31	0.1378	0.3036	0.9989	0.074*
C32	0.2622 (2)	0.27640 (11)	0.9467 (2)	0.0474 (6)
H32	0.3125	0.2763	1.0066	0.057*
C33	0.63738 (14)	0.06207 (8)	1.13095 (14)	0.0221 (4)
C34	0.60805 (16)	0.00627 (9)	1.10584 (16)	0.0287 (4)
H34	0.6007	−0.0059	1.0413	0.034*
C35	0.58935 (17)	−0.03197 (9)	1.17365 (17)	0.0338 (5)
H35	0.5676	−0.0699	1.1554	0.041*
C36	0.60237 (18)	−0.01485 (10)	1.26792 (17)	0.0364 (5)
H36	0.5884	−0.0407	1.3145	0.044*
C37	0.6355 (2)	0.03952 (11)	1.29402 (17)	0.0397 (6)
H37	0.6468	0.0509	1.3593	0.048*
C38	0.65278 (18)	0.07817 (10)	1.22583 (16)	0.0323 (5)
H38	0.6753	0.1159	1.2446	0.039*
C39	0.96499 (15)	0.10293 (9)	0.81744 (15)	0.0259 (4)
C40	0.94875 (18)	0.04766 (10)	0.78297 (17)	0.0348 (5)
H40	0.8823	0.0298	0.7782	0.042*
C41	1.0294 (2)	0.01821 (11)	0.75534 (19)	0.0420 (6)
H41	1.0174	−0.0194	0.7305	0.050*
C42	1.12631 (19)	0.04332 (11)	0.76376 (18)	0.0404 (6)
H42	1.1809	0.0233	0.7440	0.048*
C43	1.14398 (18)	0.09762 (11)	0.80098 (18)	0.0388 (6)
H43	1.2115	0.1146	0.8086	0.047*
C44	1.06373 (16)	0.12744 (10)	0.82726 (17)	0.0326 (5)
H44	1.0763	0.1650	0.8522	0.039*
C45	0.82727 (17)	0.25121 (10)	1.01486 (17)	0.0335 (5)
H45	0.8677	0.2231	0.9919	0.040*
C46	0.8785 (2)	0.28936 (12)	1.08273 (19)	0.0456 (6)
H46	0.9527	0.2871	1.1069	0.055*
C47	0.8210 (2)	0.33068 (12)	1.1151 (2)	0.0542 (7)
H47	0.8548	0.3580	1.1611	0.065*
C48	0.7130 (2)	0.33191 (12)	1.0799 (2)	0.0540 (7)
H48	0.6713	0.3599	1.1017	0.065*
C49	0.6669 (2)	0.29215 (10)	1.01310 (18)	0.0380 (5)
H49	0.5926	0.2930	0.9894	0.046*
C9	0.55584 (15)	0.13662 (8)	1.01593 (14)	0.0214 (4)

	U11	U22	U33	U12	U13	U23
Co	0.01456 (13)	0.01685 (14)	0.02065 (14)	0.00084 (9)	0.00195 (9)	0.00394 (10)
Cl	0.0259 (2)	0.0279 (3)	0.0271 (3)	−0.00221 (19)	−0.00032 (19)	−0.0017 (2)
N1	0.0166 (7)	0.0216 (8)	0.0276 (9)	0.0002 (6)	0.0028 (6)	0.0048 (7)
N2	0.0174 (7)	0.0200 (8)	0.0235 (8)	0.0014 (6)	0.0031 (6)	0.0014 (7)
N3	0.0159 (7)	0.0187 (8)	0.0217 (8)	0.0000 (6)	0.0027 (6)	0.0034 (6)
N4	0.0169 (7)	0.0215 (8)	0.0236 (8)	0.0023 (6)	0.0026 (6)	0.0066 (7)
N5	0.0226 (8)	0.0202 (8)	0.0260 (9)	−0.0007 (6)	0.0023 (7)	0.0024 (7)
C1	0.0221 (9)	0.0216 (10)	0.0291 (11)	0.0028 (7)	0.0020 (8)	0.0060 (8)
C2	0.0280 (11)	0.0250 (11)	0.0480 (14)	0.0064 (8)	0.0098 (10)	0.0139 (10)
C3	0.0255 (10)	0.0281 (12)	0.0522 (14)	0.0091 (9)	0.0093 (10)	0.0128 (10)
C4	0.0180 (9)	0.0245 (10)	0.0343 (11)	0.0047 (8)	0.0029 (8)	0.0065 (9)
C5	0.0194 (9)	0.0250 (10)	0.0367 (12)	0.0039 (8)	0.0056 (8)	0.0050 (9)
C6	0.0174 (9)	0.0236 (10)	0.0291 (10)	0.0024 (7)	0.0056 (8)	0.0010 (8)
C7	0.0207 (9)	0.0283 (11)	0.0343 (11)	0.0010 (8)	0.0109 (8)	0.0010 (9)
C8	0.0247 (10)	0.0242 (10)	0.0289 (11)	−0.0003 (8)	0.0105 (8)	0.0024 (8)
C10	0.0232 (9)	0.0185 (9)	0.0190 (9)	−0.0016 (7)	0.0032 (7)	0.0005 (7)
C11	0.0195 (9)	0.0168 (9)	0.0215 (9)	−0.0009 (7)	0.0015 (7)	0.0023 (7)
C12	0.0227 (9)	0.0212 (10)	0.0224 (10)	0.0008 (7)	0.0009 (7)	0.0060 (8)
C13	0.0184 (9)	0.0207 (10)	0.0286 (10)	0.0021 (7)	0.0026 (8)	0.0045 (8)
C14	0.0162 (8)	0.0184 (9)	0.0253 (10)	0.0006 (7)	0.0031 (7)	0.0028 (8)
C15	0.0182 (9)	0.0233 (10)	0.0269 (10)	0.0020 (7)	0.0046 (8)	0.0046 (8)
C16	0.0180 (9)	0.0259 (10)	0.0276 (10)	0.0027 (7)	0.0054 (8)	0.0072 (8)
C17	0.0255 (10)	0.0383 (13)	0.0348 (12)	0.0085 (9)	0.0122 (9)	0.0145 (10)
C18	0.0271 (10)	0.0366 (12)	0.0342 (12)	0.0057 (9)	0.0107 (9)	0.0176 (10)
C19	0.0193 (9)	0.0267 (11)	0.0269 (10)	0.0006 (8)	0.0019 (8)	0.0100 (8)
C20	0.0239 (10)	0.0241 (10)	0.0301 (11)	0.0012 (8)	0.0044 (8)	0.0104 (8)
C21	0.0223 (10)	0.0250 (11)	0.0426 (13)	0.0054 (8)	0.0088 (9)	0.0136 (9)
C22	0.0416 (12)	0.0276 (11)	0.0370 (13)	0.0061 (9)	0.0097 (10)	0.0108 (10)
C23	0.0517 (14)	0.0334 (13)	0.0425 (14)	0.0108 (11)	0.0200 (12)	0.0186 (11)
C24	0.0356 (12)	0.0293 (12)	0.0700 (18)	0.0069 (10)	0.0256 (12)	0.0217 (12)
C25	0.0351 (13)	0.0434 (15)	0.079 (2)	−0.0141 (11)	−0.0025 (13)	0.0192 (15)
C26	0.0384 (13)	0.0436 (15)	0.0570 (17)	−0.0083 (11)	−0.0063 (12)	0.0244 (13)
C27	0.0236 (10)	0.0251 (11)	0.0527 (14)	0.0047 (8)	0.0123 (10)	0.0089 (10)
C28	0.0230 (10)	0.0322 (12)	0.0625 (17)	0.0016 (9)	0.0056 (10)	0.0138 (11)
C29	0.0254 (12)	0.0413 (15)	0.088 (2)	0.0031 (10)	0.0074 (13)	0.0234 (15)
C30	0.0276 (13)	0.0456 (16)	0.111 (3)	0.0123 (11)	0.0225 (16)	0.0168 (17)
C31	0.0514 (17)	0.0533 (18)	0.090 (2)	0.0129 (14)	0.0393 (18)	0.0002 (16)
C32	0.0391 (13)	0.0458 (15)	0.0619 (18)	0.0131 (11)	0.0208 (12)	0.0046 (13)
C33	0.0200 (9)	0.0228 (10)	0.0236 (10)	0.0022 (7)	0.0055 (7)	0.0042 (8)
C34	0.0314 (11)	0.0262 (11)	0.0280 (11)	−0.0021 (8)	0.0059 (9)	0.0012 (9)
C35	0.0350 (11)	0.0224 (10)	0.0452 (13)	−0.0018 (9)	0.0119 (10)	0.0069 (10)
C36	0.0421 (13)	0.0334 (12)	0.0390 (13)	0.0072 (10)	0.0204 (11)	0.0158 (10)
C37	0.0562 (15)	0.0418 (14)	0.0246 (11)	0.0057 (11)	0.0164 (10)	0.0042 (10)
C38	0.0453 (13)	0.0263 (11)	0.0277 (11)	−0.0007 (9)	0.0133 (10)	−0.0017 (9)
C39	0.0239 (9)	0.0275 (11)	0.0281 (11)	0.0083 (8)	0.0097 (8)	0.0113 (8)
C40	0.0327 (11)	0.0311 (12)	0.0427 (13)	0.0032 (9)	0.0134 (10)	0.0058 (10)
C41	0.0487 (14)	0.0331 (13)	0.0472 (15)	0.0129 (11)	0.0175 (12)	0.0027 (11)
C42	0.0369 (12)	0.0470 (15)	0.0422 (14)	0.0220 (11)	0.0192 (10)	0.0152 (11)
C43	0.0253 (11)	0.0476 (15)	0.0463 (14)	0.0098 (10)	0.0140 (10)	0.0161 (12)
C44	0.0248 (10)	0.0334 (12)	0.0402 (13)	0.0052 (9)	0.0090 (9)	0.0091 (10)
C45	0.0259 (10)	0.0345 (12)	0.0369 (12)	−0.0043 (9)	0.0007 (9)	0.0008 (10)
C46	0.0356 (13)	0.0486 (15)	0.0461 (15)	−0.0126 (11)	−0.0036 (11)	−0.0062 (12)
C47	0.0590 (17)	0.0426 (16)	0.0528 (17)	−0.0114 (13)	−0.0038 (14)	−0.0149 (13)
C48	0.0596 (17)	0.0450 (16)	0.0520 (17)	0.0046 (13)	0.0018 (13)	−0.0198 (13)
C49	0.0392 (13)	0.0342 (13)	0.0379 (13)	0.0034 (10)	0.0038 (10)	−0.0047 (10)
C9	0.0222 (9)	0.0196 (9)	0.0230 (10)	−0.0017 (7)	0.0063 (8)	−0.0003 (8)

Co—N4	1.9498 (15)	C22—H22	0.9500
Co—N3	1.9564 (15)	C23—C24	1.365 (4)
Co—N2	1.9596 (16)	C23—H23	0.9500
Co—N1	1.9660 (16)	C24—C25	1.369 (4)
Co—N5	1.9898 (17)	C24—H24	0.9500
Co—Cl	2.2339 (6)	C25—C26	1.386 (3)
N1—C4	1.374 (2)	C25—H25	0.9500
N1—C1	1.375 (3)	C26—H26	0.9500
N2—C9	1.373 (2)	C27—C28	1.384 (3)
N2—C6	1.375 (2)	C27—C32	1.388 (4)
N3—C14	1.371 (2)	C28—C29	1.388 (3)
N3—C11	1.372 (2)	C28—H28	0.9500
N4—C19	1.361 (2)	C29—C30	1.357 (5)
N4—C16	1.377 (2)	C29—H29	0.9500
N5—C45	1.340 (3)	C30—C31	1.368 (5)
N5—C49	1.343 (3)	C30—H30	0.9500
C1—C20	1.385 (3)	C31—C32	1.395 (4)
C1—C2	1.431 (3)	C31—H31	0.9500
C2—C3	1.342 (3)	C32—H32	0.9500
C2—H2	0.9500	C33—C38	1.379 (3)
C3—C4	1.442 (3)	C33—C34	1.386 (3)
C3—H3	0.9500	C34—C35	1.384 (3)
C4—C5	1.384 (3)	C34—H34	0.9500
C5—C6	1.391 (3)	C35—C36	1.381 (3)
C5—C27	1.494 (3)	C35—H35	0.9500
C6—C7	1.434 (3)	C36—C37	1.368 (3)
C7—C8	1.343 (3)	C36—H36	0.9500
C7—H7	0.9500	C37—C38	1.388 (3)
C8—C9	1.436 (3)	C37—H37	0.9500
C8—H8	0.9500	C38—H38	0.9500
C10—C9	1.386 (3)	C39—C40	1.384 (3)
C10—C11	1.388 (3)	C39—C44	1.387 (3)
C10—C33	1.495 (3)	C40—C41	1.391 (3)
C11—C12	1.431 (3)	C40—H40	0.9500
C12—C13	1.344 (3)	C41—C42	1.374 (4)
C12—H12	0.9500	C41—H41	0.9500
C13—C14	1.432 (3)	C42—C43	1.378 (4)
C13—H13	0.9500	C42—H42	0.9500
C14—C15	1.392 (3)	C43—C44	1.382 (3)
C15—C16	1.383 (3)	C43—H43	0.9500
C15—C39	1.491 (3)	C44—H44	0.9500
C16—C17	1.434 (3)	C45—C46	1.373 (3)
C17—C18	1.345 (3)	C45—H45	0.9500
C17—H17	0.9500	C46—C47	1.371 (4)
C18—C19	1.427 (3)	C46—H46	0.9500
C18—H18	0.9500	C47—C48	1.381 (4)
C19—C20	1.390 (3)	C47—H47	0.9500
C20—C21	1.491 (3)	C48—C49	1.370 (4)
C21—C26	1.374 (3)	C48—H48	0.9500
C21—C22	1.382 (3)	C49—H49	0.9500
C22—C23	1.389 (3)
N4—Co—N3	89.45 (6)	C22—C21—C20	123.0 (2)
N4—Co—N2	179.36 (7)	C21—C22—C23	120.3 (2)
N3—Co—N2	90.57 (6)	C21—C22—H22	119.8
N4—Co—N1	90.19 (6)	C23—C22—H22	119.8
N3—Co—N1	178.93 (7)	C24—C23—C22	120.5 (2)
N2—Co—N1	89.81 (6)	C24—C23—H23	119.7
N4—Co—N5	89.39 (7)	C22—C23—H23	119.7
N3—Co—N5	90.20 (7)	C23—C24—C25	119.6 (2)
N2—Co—N5	91.25 (7)	C23—C24—H24	120.2
N1—Co—N5	88.80 (7)	C25—C24—H24	120.2
N4—Co—Cl	89.09 (5)	C24—C25—C26	120.1 (3)
N3—Co—Cl	89.85 (5)	C24—C25—H25	120.0
N2—Co—Cl	90.27 (5)	C26—C25—H25	120.0
N1—Co—Cl	91.14 (5)	C21—C26—C25	121.0 (2)
N5—Co—Cl	178.48 (5)	C21—C26—H26	119.5
C4—N1—C1	105.72 (16)	C25—C26—H26	119.5
C4—N1—Co	127.59 (13)	C28—C27—C32	118.8 (2)
C1—N1—Co	126.20 (13)	C28—C27—C5	120.8 (2)
C9—N2—C6	106.02 (15)	C32—C27—C5	120.3 (2)
C9—N2—Co	126.47 (12)	C27—C28—C29	120.5 (3)
C6—N2—Co	126.91 (13)	C27—C28—H28	119.8
C14—N3—C11	105.46 (15)	C29—C28—H28	119.8
C14—N3—Co	127.58 (13)	C30—C29—C28	120.3 (3)
C11—N3—Co	126.90 (12)	C30—C29—H29	119.9
C19—N4—C16	106.04 (16)	C28—C29—H29	119.9
C19—N4—Co	126.75 (13)	C29—C30—C31	120.4 (2)
C16—N4—Co	126.76 (13)	C29—C30—H30	119.8
C45—N5—C49	117.70 (19)	C31—C30—H30	119.8
C45—N5—Co	120.95 (15)	C30—C31—C32	120.3 (3)
C49—N5—Co	121.26 (15)	C30—C31—H31	119.9
N1—C1—C20	125.32 (18)	C32—C31—H31	119.9
N1—C1—C2	110.37 (17)	C27—C32—C31	119.8 (3)
C20—C1—C2	124.17 (19)	C27—C32—H32	120.1
C3—C2—C1	106.89 (19)	C31—C32—H32	120.1
C3—C2—H2	126.6	C38—C33—C34	118.77 (19)
C1—C2—H2	126.6	C38—C33—C10	121.28 (18)
C2—C3—C4	107.48 (18)	C34—C33—C10	119.82 (18)
C2—C3—H3	126.3	C35—C34—C33	120.8 (2)
C4—C3—H3	126.3	C35—C34—H34	119.6
N1—C4—C5	125.60 (18)	C33—C34—H34	119.6
N1—C4—C3	109.50 (17)	C36—C35—C34	119.8 (2)
C5—C4—C3	124.66 (18)	C36—C35—H35	120.1
C4—C5—C6	122.57 (18)	C34—C35—H35	120.1
C4—C5—C27	118.54 (18)	C37—C36—C35	119.8 (2)
C6—C5—C27	118.63 (18)	C37—C36—H36	120.1
N2—C6—C5	125.57 (18)	C35—C36—H36	120.1
N2—C6—C7	109.55 (17)	C36—C37—C38	120.5 (2)
C5—C6—C7	124.75 (17)	C36—C37—H37	119.8
C8—C7—C6	107.47 (17)	C38—C37—H37	119.8
C8—C7—H7	126.3	C33—C38—C37	120.3 (2)
C6—C7—H7	126.3	C33—C38—H38	119.8
C7—C8—C9	107.06 (17)	C37—C38—H38	119.8
C7—C8—H8	126.5	C40—C39—C44	118.96 (19)
C9—C8—H8	126.5	C40—C39—C15	119.36 (18)
C9—C10—C11	122.29 (17)	C44—C39—C15	121.67 (19)
C9—C10—C33	117.61 (16)	C39—C40—C41	120.2 (2)
C11—C10—C33	119.71 (17)	C39—C40—H40	119.9
N3—C11—C10	125.43 (17)	C41—C40—H40	119.9
N3—C11—C12	110.17 (16)	C42—C41—C40	120.3 (2)
C10—C11—C12	123.88 (17)	C42—C41—H41	119.8
C13—C12—C11	106.99 (17)	C40—C41—H41	119.8
C13—C12—H12	126.5	C41—C42—C43	119.8 (2)
C11—C12—H12	126.5	C41—C42—H42	120.1
C12—C13—C14	107.08 (16)	C43—C42—H42	120.1
C12—C13—H13	126.5	C42—C43—C44	120.2 (2)
C14—C13—H13	126.5	C42—C43—H43	119.9
N3—C14—C15	125.33 (17)	C44—C43—H43	119.9
N3—C14—C13	110.14 (16)	C43—C44—C39	120.5 (2)
C15—C14—C13	124.50 (17)	C43—C44—H44	119.7
C16—C15—C14	122.09 (17)	C39—C44—H44	119.7
C16—C15—C39	119.04 (17)	N5—C45—C46	122.7 (2)
C14—C15—C39	118.82 (17)	N5—C45—H45	118.6
N4—C16—C15	125.07 (18)	C46—C45—H45	118.6
N4—C16—C17	109.39 (17)	C47—C46—C45	119.0 (2)
C15—C16—C17	124.97 (18)	C47—C46—H46	120.5
C18—C17—C16	106.99 (18)	C45—C46—H46	120.5
C18—C17—H17	126.5	C46—C47—C48	118.9 (2)
C16—C17—H17	126.5	C46—C47—H47	120.5
C17—C18—C19	107.18 (18)	C48—C47—H47	120.5
C17—C18—H18	126.4	C49—C48—C47	119.0 (3)
C19—C18—H18	126.4	C49—C48—H48	120.5
N4—C19—C20	126.24 (18)	C47—C48—H48	120.5
N4—C19—C18	110.18 (17)	N5—C49—C48	122.6 (2)
C20—C19—C18	123.39 (18)	N5—C49—H49	118.7
C1—C20—C19	121.87 (18)	C48—C49—H49	118.7
C1—C20—C21	119.86 (18)	N2—C9—C10	126.52 (17)
C19—C20—C21	118.27 (18)	N2—C9—C8	109.82 (17)
C26—C21—C22	118.4 (2)	C10—C9—C8	123.58 (18)
C26—C21—C20	118.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C24—H24···Cg3i	0.95	2.79	3.543 (3)	137
C28—H28···Cg9ii	0.95	2.79	3.735 (3)	172
C35—H35···Cg2iii	0.95	2.87	3.736 (2)	152
C38—H38···Cg11iv	0.95	2.98	3.861 (3)	156
C42—H42···Cg12v	0.95	2.75	3.574 (3)	146
C49—H49···Cg6	0.95	2.35	2.931 (3)	119

Table 1

Hydrogen-bond geometry (Å, °)

Cg2, Cg3, Cg6, Cg9, Cg11 and Cg12 are the centroids of the N2/C6–C9, N3/C11–C14, Co/N1/C4–C6/N2, N5/C45–C49, C27–C32 and C33–C38 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C24—H24⋯Cg3i	0.95	2.79	3.543 (3)	137
C28—H28⋯Cg9ii	0.95	2.79	3.735 (3)	172
C35—H35⋯Cg2iii	0.95	2.87	3.736 (2)	152
C38—H38⋯Cg11iv	0.95	2.98	3.861 (3)	156
C42—H42⋯Cg12v	0.95	2.75	3.574 (3)	146
C49—H49⋯Cg6	0.95	2.35	2.931 (3)	119

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