Crystal structure and magnetic properties of a linear tetra­nuclear Co^II cluster

Polynuclear complexes are an important class of inorganic functional materials and are of interest particularly for their applications in molecular magnets. Multidentate chelating ligands play an important role in the design and syntheses of polynuclear metal clusters. A novel linear tetra­nuclear Co^II cluster, namely bis­{μ₃-(E)-2-[(2-oxido­benzyl­idene)amino]­phenolato}bis{μ₂-(E)-2-[(2-oxido­benzyl­idene)amino]­phenolato}bis­(1,10-phenanthroline)tetra­cobalt(II), [Co₄(C₁₄H₁₁NO₂)₄(C₁₂H₈N₂)₂], was prepared under solvothermal conditions through a mixed-ligand synthetic strategy. The structure was determined by X-ray single-crystal diffraction and bulk purity was confirmed by powder X-ray diffraction. The complex molecule has a centrosymmetric tetranuclear chain-like structure and the four Co^II ions are located in two different coordination environments. The Co^II ions at the ends of the chain are in a slightly distorted octa­hedral geometry, while the two inner Co^II ions are in five-coordinate distorted trigonal bipyramidal environments. A magnetic study reveals ferro­magnetic Co^II...Co^II exchange inter­actions for the complex.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXL2014 (Sheldrick, 2015) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Bis{µ₃-(E)-2-[(2-oxidobenzylidene)amino]phenolato}bis{µ₂-(E)-2-[(2-oxidobenzylidene)amino]phenolato}bis(1,10-phenanthroline)tetracobalt(II)

Crystal data

[Co4(C14H11NO2)4(C12H8N2)2]	F(000) = 1536
Mr = 1497.08	Dx = 1.467 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.6762 (12) Å	Cell parameters from 3972 reflections
b = 18.3463 (19) Å	θ = 2.2–26.7°
c = 16.0700 (16) Å	µ = 1.03 mm^−1
β = 100.105 (2)°	T = 296 K
V = 3389.0 (6) Å^3	Block, red
Z = 2	0.28 × 0.27 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer	4856 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
φ and ω scans	θmax = 27.6°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→12
Tmin = 0.762, Tmax = 0.837	k = −23→23
20250 measured reflections	l = −17→20
7686 independent reflections

Refinement

Refinement on F^2	12 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 0.5996P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
7686 reflections	Δρmax = 0.44 e Å^−3
451 parameters	Δρmin = −0.34 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Co1	0.14825 (3)	1.00703 (2)	0.76055 (2)	0.03500 (10)
Co2	0.10258 (3)	1.00239 (2)	0.94943 (2)	0.03444 (10)
O1	0.26236 (16)	1.04966 (9)	0.69696 (11)	0.0448 (4)
O3	0.20859 (15)	1.05578 (9)	0.88408 (10)	0.0410 (4)
O2	0.03870 (15)	0.96306 (9)	0.83597 (10)	0.0380 (4)
N3	0.02779 (19)	0.96695 (12)	0.65045 (12)	0.0393 (5)
C40	−0.0498 (2)	1.01739 (14)	0.61554 (15)	0.0391 (6)
C32	−0.1348 (2)	1.00345 (17)	0.54336 (16)	0.0502 (7)
N2	0.2385 (2)	0.97663 (12)	1.04056 (13)	0.0445 (6)
N1	0.25038 (19)	0.91454 (11)	0.78638 (12)	0.0386 (5)
C21	0.3350 (3)	1.01125 (15)	1.05133 (18)	0.0537 (8)
H21	0.3888	0.9991	1.0991	0.064*
C23	0.0431 (2)	0.86301 (13)	1.03053 (15)	0.0371 (6)
C16	0.3083 (2)	1.08661 (13)	0.91744 (16)	0.0374 (6)
C9	0.0041 (2)	0.89391 (14)	0.81854 (15)	0.0401 (6)
N4	0.03553 (19)	1.09789 (11)	0.72574 (13)	0.0403 (5)
C24	−0.0221 (2)	0.80061 (14)	1.00884 (16)	0.0460 (7)
H24	−0.0988	0.8045	0.9813	0.055*
C2	0.3626 (2)	1.02430 (14)	0.68656 (16)	0.0409 (6)
C39	−0.0439 (2)	1.08801 (15)	0.65431 (16)	0.0415 (6)
C8	0.0875 (3)	0.83888 (14)	0.81937 (15)	0.0428 (7)
C7	0.3487 (2)	0.90574 (15)	0.76272 (17)	0.0469 (7)
H7	0.3868	0.8619	0.7779	0.056*
C22	0.1564 (3)	0.85686 (14)	1.07486 (16)	0.0449 (7)
C29	0.0204 (3)	0.90131 (15)	0.61623 (17)	0.0492 (7)
H29	0.0730	0.8659	0.6403	0.059*
C10	−0.1129 (3)	0.87649 (17)	0.79715 (17)	0.0530 (8)
H10	−0.1690	0.9127	0.7957	0.064*
C13	0.0513 (3)	0.76790 (16)	0.80081 (17)	0.0575 (8)
H13	0.1065	0.7312	0.8020	0.069*
C1	0.4069 (2)	0.95586 (15)	0.71535 (18)	0.0486 (7)
C38	0.0385 (3)	1.16149 (15)	0.76449 (19)	0.0531 (8)
H38	0.0905	1.1680	0.8148	0.064*
C14	0.2145 (2)	0.85819 (14)	0.84232 (17)	0.0450 (7)
H14A	0.2303	0.8756	0.9002	0.054*
H14B	0.2607	0.8146	0.8393	0.054*
C18	0.4575 (3)	1.17550 (17)	0.9055 (2)	0.0604 (8)
H18	0.4863	1.2118	0.8744	0.072*
C27	0.2031 (3)	0.78794 (17)	1.0919 (2)	0.0638 (9)
H27	0.2795	0.7834	1.1199	0.077*
C15	0.3700 (2)	1.06750 (14)	0.99728 (17)	0.0471 (7)
C35	−0.1198 (3)	1.14308 (18)	0.61808 (19)	0.0568 (8)
C37	−0.0338 (3)	1.21925 (17)	0.7325 (2)	0.0710 (10)
H37	−0.0294	1.2635	0.7611	0.085*
C12	−0.0644 (4)	0.75098 (19)	0.7808 (2)	0.0697 (10)
H12	−0.0877	0.7030	0.7691	0.084*
C25	0.0264 (3)	0.73264 (16)	1.0280 (2)	0.0596 (8)
H25	−0.0181	0.6910	1.0134	0.072*
C17	0.3560 (2)	1.14068 (15)	0.87249 (17)	0.0497 (7)
H17	0.3176	1.1533	0.8187	0.060*
C34	−0.2027 (3)	1.1272 (2)	0.5433 (2)	0.0713 (10)
H34	−0.2522	1.1638	0.5183	0.086*
C30	−0.0617 (3)	0.88225 (17)	0.54616 (18)	0.0590 (8)
H30	−0.0642	0.8350	0.5249	0.071*
C28	0.2201 (3)	0.92471 (16)	1.10786 (18)	0.0600 (8)
H28A	0.1766	0.9490	1.1459	0.072*
H28B	0.2952	0.9112	1.1403	0.072*
C3	0.4324 (3)	1.06740 (16)	0.6422 (2)	0.0592 (8)
H3	0.4049	1.1127	0.6217	0.071*
C26	0.1391 (3)	0.72611 (17)	1.0682 (2)	0.0678 (10)
H26	0.1722	0.6803	1.0794	0.081*
C19	0.5173 (3)	1.15712 (19)	0.9842 (2)	0.0736 (11)
H19	0.5855	1.1813	1.0072	0.088*
C36	−0.1106 (3)	1.21043 (19)	0.6593 (2)	0.0743 (11)
H36	−0.1571	1.2492	0.6367	0.089*
C20	0.4749 (3)	1.10308 (18)	1.0276 (2)	0.0726 (10)
H20	0.5172	1.0891	1.0796	0.087*
C11	−0.1459 (3)	0.8053 (2)	0.7780 (2)	0.0685 (10)
H11	−0.2244	0.7940	0.7630	0.082*
C31	−0.1381 (3)	0.93326 (19)	0.50905 (19)	0.0608 (9)
H31	−0.1922	0.9216	0.4612	0.073*
C6	0.5174 (3)	0.93459 (19)	0.7007 (3)	0.0897 (13)
H6	0.5470	0.8896	0.7208	0.108*
C33	−0.2099 (3)	1.0609 (2)	0.5090 (2)	0.0669 (9)
H33	−0.2657	1.0520	0.4612	0.080*
C4	0.5383 (3)	1.0446 (2)	0.6287 (3)	0.0903 (13)
H4	0.5817	1.0745	0.5992	0.108*
C5	0.5826 (4)	0.9776 (2)	0.6580 (3)	0.1011 (14)
H5	0.6552	0.9623	0.6487	0.121*
O4	0.00007 (15)	0.92934 (9)	1.00743 (10)	0.0414 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0362 (2)	0.0383 (2)	0.03062 (18)	−0.00059 (15)	0.00608 (15)	0.00201 (15)
Co2	0.03541 (19)	0.03871 (19)	0.03009 (17)	−0.00143 (15)	0.00822 (14)	0.00071 (15)
O1	0.0421 (11)	0.0496 (11)	0.0443 (10)	0.0028 (9)	0.0118 (9)	0.0110 (9)
O3	0.0380 (10)	0.0513 (11)	0.0335 (9)	−0.0128 (8)	0.0055 (8)	0.0019 (8)
O2	0.0410 (10)	0.0408 (10)	0.0333 (9)	−0.0085 (8)	0.0093 (8)	−0.0034 (8)
N3	0.0422 (13)	0.0448 (13)	0.0311 (11)	−0.0025 (10)	0.0072 (10)	0.0017 (10)
C40	0.0340 (14)	0.0538 (17)	0.0313 (13)	−0.0009 (12)	0.0109 (11)	0.0059 (12)
C32	0.0380 (15)	0.078 (2)	0.0352 (14)	−0.0022 (15)	0.0082 (12)	0.0070 (15)
N2	0.0501 (15)	0.0440 (13)	0.0368 (12)	−0.0088 (11)	0.0006 (11)	0.0084 (10)
N1	0.0386 (13)	0.0414 (12)	0.0355 (12)	−0.0011 (10)	0.0062 (10)	0.0025 (9)
C21	0.0536 (19)	0.0528 (18)	0.0467 (16)	−0.0161 (14)	−0.0133 (14)	0.0115 (13)
C23	0.0475 (16)	0.0360 (14)	0.0309 (13)	0.0008 (12)	0.0156 (12)	0.0027 (11)
C16	0.0373 (15)	0.0369 (14)	0.0379 (14)	−0.0061 (11)	0.0065 (12)	−0.0045 (11)
C9	0.0477 (17)	0.0473 (16)	0.0263 (13)	−0.0135 (13)	0.0096 (12)	−0.0020 (11)
N4	0.0440 (14)	0.0411 (13)	0.0386 (12)	0.0009 (10)	0.0145 (11)	0.0010 (10)
C24	0.0470 (19)	0.0440 (16)	0.0473 (16)	−0.0065 (13)	0.0089 (14)	0.0011 (13)
C2	0.0408 (16)	0.0430 (15)	0.0401 (15)	−0.0068 (12)	0.0105 (13)	−0.0030 (12)
C39	0.0375 (15)	0.0524 (16)	0.0376 (15)	0.0082 (12)	0.0148 (13)	0.0080 (12)
C8	0.0572 (19)	0.0420 (15)	0.0304 (13)	−0.0112 (13)	0.0114 (13)	0.0006 (11)
C7	0.0478 (18)	0.0407 (15)	0.0526 (17)	0.0079 (13)	0.0098 (15)	0.0031 (13)
C22	0.0497 (18)	0.0446 (16)	0.0400 (15)	−0.0057 (13)	0.0062 (13)	0.0110 (12)
C29	0.062 (2)	0.0486 (17)	0.0370 (15)	−0.0044 (15)	0.0082 (14)	0.0002 (13)
C10	0.0478 (18)	0.067 (2)	0.0455 (16)	−0.0170 (15)	0.0112 (14)	−0.0058 (14)
C13	0.083 (3)	0.0477 (18)	0.0458 (17)	−0.0141 (16)	0.0215 (17)	−0.0037 (14)
C1	0.0449 (17)	0.0470 (16)	0.0578 (18)	0.0007 (13)	0.0197 (15)	0.0020 (14)
C38	0.062 (2)	0.0455 (17)	0.0548 (18)	0.0008 (15)	0.0195 (16)	−0.0020 (14)
C14	0.0518 (18)	0.0404 (15)	0.0438 (15)	0.0022 (13)	0.0113 (14)	0.0076 (12)
C18	0.057 (2)	0.0593 (19)	0.063 (2)	−0.0240 (16)	0.0057 (17)	0.0101 (16)
C27	0.0483 (19)	0.066 (2)	0.076 (2)	0.0021 (16)	0.0052 (17)	0.0322 (17)
C15	0.0467 (17)	0.0449 (16)	0.0455 (16)	−0.0125 (13)	−0.0031 (14)	0.0074 (13)
C35	0.054 (2)	0.069 (2)	0.0504 (18)	0.0242 (16)	0.0193 (16)	0.0100 (16)
C37	0.090 (3)	0.0470 (19)	0.082 (3)	0.0181 (18)	0.034 (2)	−0.0019 (17)
C12	0.098 (3)	0.054 (2)	0.061 (2)	−0.034 (2)	0.024 (2)	−0.0138 (16)
C25	0.074 (2)	0.0398 (17)	0.066 (2)	−0.0083 (15)	0.0145 (18)	0.0016 (14)
C17	0.0478 (18)	0.0573 (18)	0.0420 (16)	−0.0133 (14)	0.0021 (14)	0.0104 (13)
C34	0.054 (2)	0.103 (3)	0.056 (2)	0.034 (2)	0.0076 (18)	0.020 (2)
C30	0.078 (2)	0.0572 (19)	0.0413 (17)	−0.0182 (17)	0.0083 (17)	−0.0044 (14)
C28	0.067 (2)	0.0634 (18)	0.0448 (16)	−0.0187 (15)	−0.0025 (15)	0.0178 (14)
C3	0.060 (2)	0.0514 (18)	0.072 (2)	−0.0064 (15)	0.0286 (18)	0.0012 (15)
C26	0.075 (3)	0.0424 (18)	0.090 (3)	0.0086 (17)	0.027 (2)	0.0180 (17)
C19	0.063 (2)	0.075 (2)	0.073 (2)	−0.0365 (18)	−0.0156 (18)	0.0180 (18)
C36	0.083 (3)	0.071 (2)	0.073 (2)	0.039 (2)	0.027 (2)	0.0178 (19)
C20	0.066 (2)	0.074 (2)	0.065 (2)	−0.0317 (18)	−0.0223 (17)	0.0241 (18)
C11	0.067 (2)	0.081 (3)	0.059 (2)	−0.042 (2)	0.0152 (18)	−0.0163 (18)
C31	0.058 (2)	0.085 (2)	0.0378 (16)	−0.0241 (18)	0.0034 (15)	−0.0040 (16)
C6	0.073 (3)	0.063 (2)	0.150 (4)	0.0175 (19)	0.066 (3)	0.023 (2)
C33	0.044 (2)	0.105 (3)	0.0487 (19)	0.0140 (19)	0.0011 (16)	0.0081 (19)
C4	0.083 (3)	0.066 (2)	0.140 (4)	−0.003 (2)	0.070 (3)	0.017 (2)
C5	0.077 (2)	0.094 (3)	0.149 (3)	0.011 (2)	0.065 (3)	0.018 (2)
O4	0.0463 (11)	0.0359 (10)	0.0456 (10)	0.0019 (8)	0.0180 (9)	0.0061 (8)

Geometric parameters (Å, º)

Co1—O1	1.9772 (17)	C29—H29	0.9300
Co1—O2	2.0735 (16)	C10—C11	1.381 (4)
Co1—N1	2.074 (2)	C10—H10	0.9300
Co1—N4	2.137 (2)	C13—C12	1.368 (4)
Co1—O3	2.1786 (17)	C13—H13	0.9300
Co1—N3	2.185 (2)	C1—C6	1.407 (4)
Co2—O4^i	1.9434 (17)	C38—C37	1.396 (4)
Co2—O2	1.9810 (16)	C38—H38	0.9300
Co2—O3	2.0127 (16)	C14—H14A	0.9700
Co2—N2	2.018 (2)	C14—H14B	0.9700
Co2—O4	2.1187 (16)	C18—C17	1.369 (4)
O1—C2	1.297 (3)	C18—C19	1.375 (4)
O3—C16	1.320 (3)	C18—H18	0.9300
O2—C9	1.346 (3)	C27—C26	1.375 (4)
N3—C29	1.320 (3)	C27—H27	0.9300
N3—C40	1.347 (3)	C15—C20	1.397 (4)
C40—C32	1.411 (4)	C35—C36	1.397 (5)
C40—C39	1.434 (4)	C35—C34	1.435 (4)
C32—C31	1.399 (4)	C37—C36	1.357 (5)
C32—C33	1.420 (4)	C37—H37	0.9300
N2—C21	1.278 (3)	C12—C11	1.374 (5)
N2—C28	1.485 (3)	C12—H12	0.9300
N1—C7	1.281 (3)	C25—C26	1.365 (4)
N1—C14	1.478 (3)	C25—H25	0.9300
C21—C15	1.453 (4)	C17—H17	0.9300
C21—H21	0.9300	C34—C33	1.331 (5)
C23—O4	1.344 (3)	C34—H34	0.9300
C23—C22	1.392 (4)	C30—C31	1.357 (4)
C23—C24	1.385 (3)	C30—H30	0.9300
C16—C15	1.402 (4)	C28—H28A	0.9700
C16—C17	1.399 (3)	C28—H28B	0.9700
C9—C10	1.386 (4)	C3—C4	1.359 (4)
C9—C8	1.402 (4)	C3—H3	0.9300
N4—C38	1.320 (3)	C26—H26	0.9300
N4—C39	1.356 (3)	C19—C20	1.355 (4)
C24—C25	1.382 (4)	C19—H19	0.9300
C24—H24	0.9300	C36—H36	0.9300
C2—C1	1.405 (4)	C20—H20	0.9300
C2—C3	1.414 (4)	C11—H11	0.9300
C39—C35	1.401 (4)	C31—H31	0.9300
C8—C13	1.385 (4)	C6—C5	1.362 (5)
C8—C14	1.506 (4)	C6—H6	0.9300
C7—C1	1.438 (4)	C33—H33	0.9300
C7—H7	0.9300	C4—C5	1.383 (5)
C22—C27	1.385 (4)	C4—H4	0.9300
C22—C28	1.499 (4)	C5—H5	0.9300
C29—C30	1.389 (4)	O4—Co2^i	1.9435 (17)
O1—Co1—O2	175.37 (7)	C12—C13—H13	119.5
O1—Co1—N1	90.64 (8)	C8—C13—H13	119.5
O2—Co1—N1	87.52 (7)	C2—C1—C6	119.2 (3)
O1—Co1—N4	89.77 (7)	C2—C1—C7	124.4 (2)
O2—Co1—N4	92.39 (7)	C6—C1—C7	116.4 (3)
N1—Co1—N4	175.54 (8)	N4—C38—C37	122.2 (3)
O1—Co1—O3	99.73 (7)	N4—C38—H38	118.9
O2—Co1—O3	76.19 (6)	C37—C38—H38	118.9
N1—Co1—O3	94.07 (7)	N1—C14—C8	112.8 (2)
N4—Co1—O3	90.24 (7)	N1—C14—H14A	109.0
O1—Co1—N3	96.37 (8)	C8—C14—H14A	109.0
O2—Co1—N3	88.10 (7)	N1—C14—H14B	109.0
N1—Co1—N3	98.77 (8)	C8—C14—H14B	109.0
N4—Co1—N3	76.77 (8)	H14A—C14—H14B	107.8
O3—Co1—N3	159.25 (8)	C17—C18—C19	120.4 (3)
O4^i—Co2—O2	114.01 (7)	C17—C18—H18	119.8
O4^i—Co2—O3	110.28 (7)	C19—C18—H18	119.8
O2—Co2—O3	82.17 (7)	C22—C27—C26	121.4 (3)
O4^i—Co2—N2	110.36 (8)	C22—C27—H27	119.3
O2—Co2—N2	134.74 (8)	C26—C27—H27	119.3
O3—Co2—N2	90.87 (8)	C16—C15—C20	118.7 (2)
O4^i—Co2—O4	79.59 (7)	C16—C15—C21	124.8 (2)
O2—Co2—O4	91.38 (7)	C20—C15—C21	116.4 (2)
O3—Co2—O4	169.75 (7)	C36—C35—C39	116.8 (3)
N2—Co2—O4	88.04 (8)	C36—C35—C34	124.2 (3)
C2—O1—Co1	129.03 (16)	C39—C35—C34	119.0 (3)
C16—O3—Co2	125.15 (15)	C36—C37—C38	119.6 (3)
C16—O3—Co1	131.84 (15)	C36—C37—H37	120.2
Co2—O3—Co1	98.36 (7)	C38—C37—H37	120.2
C9—O2—Co2	125.85 (15)	C13—C12—C11	119.5 (3)
C9—O2—Co1	116.02 (14)	C13—C12—H12	120.2
Co2—O2—Co1	103.01 (7)	C11—C12—H12	120.2
C29—N3—C40	117.6 (2)	C26—C25—C24	120.5 (3)
C29—N3—Co1	129.04 (19)	C26—C25—H25	119.7
C40—N3—Co1	113.36 (17)	C24—C25—H25	119.7
N3—C40—C32	122.8 (3)	C18—C17—C16	121.8 (3)
N3—C40—C39	117.5 (2)	C18—C17—H17	119.1
C32—C40—C39	119.6 (2)	C16—C17—H17	119.1
C31—C32—C40	117.3 (3)	C33—C34—C35	121.1 (3)
C31—C32—C33	123.9 (3)	C33—C34—H34	119.4
C40—C32—C33	118.8 (3)	C35—C34—H34	119.4
C21—N2—C28	117.2 (2)	C31—C30—C29	119.3 (3)
C21—N2—Co2	122.97 (18)	C31—C30—H30	120.3
C28—N2—Co2	118.87 (18)	C29—C30—H30	120.3
C7—N1—C14	117.2 (2)	N2—C28—C22	113.7 (2)
C7—N1—Co1	123.89 (18)	N2—C28—H28A	108.8
C14—N1—Co1	118.66 (16)	C22—C28—H28A	108.8
N2—C21—C15	127.3 (3)	N2—C28—H28B	108.8
N2—C21—H21	116.4	C22—C28—H28B	108.8
C15—C21—H21	116.4	H28A—C28—H28B	107.7
O4—C23—C22	119.4 (2)	C2—C3—C4	122.0 (3)
O4—C23—C24	121.1 (3)	C2—C3—H3	119.0
C22—C23—C24	119.5 (2)	C4—C3—H3	119.0
O3—C16—C15	122.7 (2)	C25—C26—C27	119.4 (3)
O3—C16—C17	119.8 (2)	C25—C26—H26	120.3
C15—C16—C17	117.6 (2)	C27—C26—H26	120.3
O2—C9—C10	121.0 (3)	C20—C19—C18	118.7 (3)
O2—C9—C8	119.6 (2)	C20—C19—H19	120.6
C10—C9—C8	119.3 (3)	C18—C19—H19	120.6
C38—N4—C39	118.4 (2)	C37—C36—C35	120.0 (3)
C38—N4—Co1	127.0 (2)	C37—C36—H36	120.0
C39—N4—Co1	114.58 (17)	C35—C36—H36	120.0
C23—C24—C25	120.3 (3)	C19—C20—C15	122.6 (3)
C23—C24—H24	119.9	C19—C20—H20	118.7
C25—C24—H24	119.9	C15—C20—H20	118.7
O1—C2—C1	124.5 (2)	C12—C11—C10	121.0 (3)
O1—C2—C3	118.5 (2)	C12—C11—H11	119.5
C1—C2—C3	117.0 (3)	C10—C11—H11	119.5
N4—C39—C35	123.0 (3)	C30—C31—C32	119.4 (3)
N4—C39—C40	117.5 (2)	C30—C31—H31	120.3
C35—C39—C40	119.5 (3)	C32—C31—H31	120.3
C13—C8—C9	119.3 (3)	C5—C6—C1	122.2 (3)
C13—C8—C14	121.6 (3)	C5—C6—H6	118.9
C9—C8—C14	119.1 (2)	C1—C6—H6	118.9
N1—C7—C1	127.4 (3)	C34—C33—C32	121.8 (3)
N1—C7—H7	116.3	C34—C33—H33	119.1
C1—C7—H7	116.3	C32—C33—H33	119.1
C23—C22—C27	118.8 (3)	C5—C4—C3	121.0 (3)
C23—C22—C28	118.8 (3)	C5—C4—H4	119.5
C27—C22—C28	122.3 (3)	C3—C4—H4	119.5
N3—C29—C30	123.5 (3)	C6—C5—C4	118.6 (3)
N3—C29—H29	118.2	C6—C5—H5	120.7
C30—C29—H29	118.2	C4—C5—H5	120.7
C9—C10—C11	119.8 (3)	C23—O4—Co2^i	135.18 (14)
C9—C10—H10	120.1	C23—O4—Co2	118.77 (15)
C11—C10—H10	120.1	Co2^i—O4—Co2	100.41 (7)
C12—C13—C8	121.0 (3)
C29—N3—C40—C32	−2.1 (4)	C13—C8—C14—N1	123.4 (3)
Co1—N3—C40—C32	179.26 (19)	C9—C8—C14—N1	−58.0 (3)
C29—N3—C40—C39	178.2 (2)	C23—C22—C27—C26	−2.0 (4)
Co1—N3—C40—C39	−0.5 (3)	C28—C22—C27—C26	173.5 (3)
N3—C40—C32—C31	1.5 (4)	O3—C16—C15—C20	−179.9 (3)
C39—C40—C32—C31	−178.8 (2)	C17—C16—C15—C20	0.0 (4)
N3—C40—C32—C33	−177.5 (2)	O3—C16—C15—C21	1.8 (4)
C39—C40—C32—C33	2.3 (4)	C17—C16—C15—C21	−178.2 (3)
C28—N2—C21—C15	−176.1 (3)	N2—C21—C15—C16	−8.8 (5)
Co2—N2—C21—C15	−7.5 (5)	N2—C21—C15—C20	172.9 (3)
Co2—O3—C16—C15	20.3 (3)	N4—C39—C35—C36	−0.1 (4)
Co1—O3—C16—C15	−130.0 (2)	C40—C39—C35—C36	179.3 (3)
Co2—O3—C16—C17	−159.69 (19)	N4—C39—C35—C34	−178.8 (3)
Co1—O3—C16—C17	50.0 (3)	C40—C39—C35—C34	0.6 (4)
Co2—O2—C9—C10	107.2 (2)	N4—C38—C37—C36	0.3 (5)
Co1—O2—C9—C10	−121.4 (2)	C8—C13—C12—C11	0.8 (5)
Co2—O2—C9—C8	−74.8 (3)	C23—C24—C25—C26	−0.2 (4)
Co1—O2—C9—C8	56.6 (3)	C19—C18—C17—C16	1.1 (5)
O4—C23—C24—C25	175.5 (2)	O3—C16—C17—C18	178.3 (3)
C22—C23—C24—C25	−2.6 (4)	C15—C16—C17—C18	−1.7 (4)
Co1—O1—C2—C1	4.9 (4)	C36—C35—C34—C33	−177.3 (3)
Co1—O1—C2—C3	−176.14 (19)	C39—C35—C34—C33	1.3 (5)
C38—N4—C39—C35	2.6 (4)	N3—C29—C30—C31	1.0 (4)
Co1—N4—C39—C35	−175.3 (2)	C21—N2—C28—C22	−142.7 (3)
C38—N4—C39—C40	−176.9 (2)	Co2—N2—C28—C22	48.2 (3)
Co1—N4—C39—C40	5.2 (3)	C23—C22—C28—N2	−62.4 (4)
N3—C40—C39—N4	−3.2 (3)	C27—C22—C28—N2	122.2 (3)
C32—C40—C39—N4	177.1 (2)	O1—C2—C3—C4	−179.9 (3)
N3—C40—C39—C35	177.4 (2)	C1—C2—C3—C4	−0.9 (5)
C32—C40—C39—C35	−2.4 (4)	C24—C25—C26—C27	2.0 (5)
O2—C9—C8—C13	−179.6 (2)	C22—C27—C26—C25	−0.9 (5)
C10—C9—C8—C13	−1.6 (4)	C17—C18—C19—C20	1.3 (6)
O2—C9—C8—C14	1.8 (3)	C38—C37—C36—C35	2.2 (5)
C10—C9—C8—C14	179.8 (2)	C39—C35—C36—C37	−2.3 (5)
C14—N1—C7—C1	−173.7 (3)	C34—C35—C36—C37	176.3 (3)
Co1—N1—C7—C1	0.1 (4)	C18—C19—C20—C15	−3.0 (6)
O4—C23—C22—C27	−174.5 (2)	C16—C15—C20—C19	2.4 (6)
C24—C23—C22—C27	3.7 (4)	C21—C15—C20—C19	−179.3 (4)
O4—C23—C22—C28	9.9 (4)	C13—C12—C11—C10	−1.6 (5)
C24—C23—C22—C28	−171.9 (2)	C9—C10—C11—C12	0.8 (5)
C40—N3—C29—C30	0.8 (4)	C29—C30—C31—C32	−1.7 (4)
Co1—N3—C29—C30	179.2 (2)	C40—C32—C31—C30	0.5 (4)
O2—C9—C10—C11	178.8 (2)	C33—C32—C31—C30	179.4 (3)
C8—C9—C10—C11	0.8 (4)	C2—C1—C6—C5	−1.2 (6)
C9—C8—C13—C12	0.8 (4)	C7—C1—C6—C5	−178.8 (4)
C14—C8—C13—C12	179.4 (3)	C35—C34—C33—C32	−1.5 (5)
O1—C2—C1—C6	−179.6 (3)	C31—C32—C33—C34	−179.2 (3)
C3—C2—C1—C6	1.4 (4)	C40—C32—C33—C34	−0.3 (5)
O1—C2—C1—C7	−2.2 (5)	C2—C3—C4—C5	0.0 (6)
C3—C2—C1—C7	178.8 (3)	C1—C6—C5—C4	0.4 (7)
N1—C7—C1—C2	−0.4 (5)	C3—C4—C5—C6	0.2 (7)
N1—C7—C1—C6	177.1 (3)	C22—C23—O4—Co2^i	−100.5 (3)
C39—N4—C38—C37	−2.7 (4)	C24—C23—O4—Co2^i	81.4 (3)
Co1—N4—C38—C37	174.9 (2)	C22—C23—O4—Co2	47.2 (3)
C7—N1—C14—C8	−138.6 (2)	C24—C23—O4—Co2	−130.9 (2)
Co1—N1—C14—C8	47.2 (3)

Symmetry code: (i) −x, −y+2, −z+2.