μ-Peroxo-bis­[trans-chloro(1,4,8,11-tetra­aza­cyclo­tetra­decane)­cobalt(III)] bis­(tetra­phenyl­borate) diacetone solvate

The title complex, [Co₂Cl₂(μ-O₂)(cyclam)₂](C₂₄H₂₀B)₂·2Me₂CO, was obtained when [Co(cyclam)Cl₂](BPh₄)₂ was crystallized from acetone in air; cyclam is 1,4,8,11-tetraazacyclo­tetradecane, C₁₀H₂₄N₄. The peroxo O–O moiety straddles a crystallographic centre of inversion (the two octahedral Co atoms are symmetrically bridged by the O₂ moiety), hence only half of the complex cation is in the asymmetric unit. A comparison of the O—O [1.483 (3) Å], Co—Cl [2.2647 (8) Å] and Co—O [1.894 (2) Å] bond lengths with similar bonds in previously determined structures indicates the oxidation of Co^II to Co^III during the crystallization process. In the crystal lattice, cation dimers are encapsulated by six [BPh₄]⁻ anions, with C—H...π hydrogen bonds between the cyclam methyl­ene groups and the phenyl rings of the anion.

S1. Comment

Whilst tetraaza macrocyclic ligands have been extensively studied for several decades, their complexes still attract significant attention. This continued interest is due to the wide range of physical and chemical properties exhibited by these materials, one relevant example being the ability to bind dioxygen to Co^II or Fe^II centres (Busch & Alcock, 1994). An extensive series of saturated and unsaturated macrocycles is known, with one of the more widely used ligands being 1,4,8,11-tetraazacyclotetradecane, also known as cyclam (McAuley & Subramanian, 2000; Melson, 1979; Donnelly & Zimmer, 1999). As an `innocent' ligand, cyclam is often used to coordinatively saturate the four equatorial sites of an octahedral centre, without influencing the nature of the metal centre. Thus, whilst investigating a series of complexes with axial hydrogen-bonding functionality, the complex [Co(cyclam)Cl₂][BPh₄]₂ was crystallized in air, yielding the oxygenated title compound, [Cl(cyclam)Co(µ₂-O₂)Co(cyclam)Cl](BPh₄)₂^.2Me₂CO, (I). A search of the Cambridge Structural Database (CSD; Allen & Kennard, 1993) revealed 34 structures containing analogous Co–(µ₂-O₂)–Co moieties. However, whilst 21 of these structures contain polydentate aminoalkane ligands (for example, ethylenetriamine or ethylenediamine), no saturated macrocyclic complexes have been reported.

The molecular structure of the cobalt complex cation of (I) comprises two octahedral Co(cyclam)Cl moieties bridged by a dioxygen molecule (Fig. 1). The O—O bond straddles a crystallographic centre of inversion, hence only half of the cation, one anion and one solvent molecule are observed in the asymmetric unit.

With redox-active ligands (in this instance O₂) bridging two Co atoms, there is some difficulty in assigning formal oxidation states to the metal centres. Thus, the analogous structures in the CSD were examined to aid in the characterization of (I). Of the 21 structures, 12 are assigned Co^II–Co^II, three Co^III–Co^III, three Co^II—Co^III, while three are denoted Co^II–Co^I. In the structure of (I), either the Co atoms are both in the +3 oxidation state and bridged by a peroxide O₂^2- molecule or there exists a mixed-valence Co^II–Co^III system, with the atoms bridged by superoxide O₂^-. However, the complex is characterized as comprising two peroxo-bridged octahedral Co^III atoms, due to two main features of the molecular structure supporting this assignation. Firstly, the O—O distance of (I) is 1.483 (3) Å, indicating a doubly-bridging peroxo species, [doubly-bridging peroxo complexes typically have O—O separations in the range 1.44–1.49 Å, compared with analogous superoxo values in the range 1.26–1.36 Å (Greenwood & Earnshaw, 1984)]. Secondly, the Co—Cl bond length of 2.2647 (8) Å supports the presence of Co^III over Co^II (Orpen, 1989). The Co—O distance of 1.894 (2) Å does not assist this characterization, as the comparable structures in the CSD all have Co—O bond lengths in the range 1.742–1.947 Å. Of these, only one outlying structure {the Co^II–Co^I species [Co₂(en)₄(µ₂-OH)(µ₂-O₂)]I₃^.H₂O; CSD refcode BATTAR (Bigoli et al., 1981)]} has a Co—O length below 1.842 Å. Thus, there is no significant correlation between assigned cobalt oxidation states and Co—O bond length.

Interestingly, the O—O—Co angle of 110.2 (2)° in (I) is lower than the value of 120° expected for an sp²-hybridized O atom binding via a lone pair. The reason for this contraction is not readily apparent, especially as the cyclam ligands are well separated (Co—N₄ mean planes are ca 4.30 Å apart). However, the geometry of the peroxide coordination here is consistent with the related structures in the CSD, which have O—O—Co values ranging from 109.8° in [Co₂(µ₂-O₂)L₂](ClO₄)₄ [L = N,N',N''-tris(2-aminoethyl)ethane-1,2-diamine; CSD refcode VIRCAA (Gatehouse et al., 1991)] to 120.6° in [Co₂(µ₂-O₂)L₂{OC(NMe)₂}₂] [L = N,N'-ethylenebis(salicylideneiminato); refcode DOESCF10 (Calligaris et al., 1970)]. Evidently, the nature of this coordination is flexible, with small variations in local geometry permitted.

The Co—N distances of (I) are in the range 1.961 (2)–1.978 (2) Å, with the angles about the cobalt centre close to ideal octahedral values. All intramolecular bond lengths and angles for the tetraphenylborate anion and acetone solvent molecules are as expected.

The crystal lattice of (I) comprises a body-centred array of cations, with the long axis of the dimers aligned parallel to the z axis of the unit cell. The tetraphenylborate anions and acetone solvent molecules pack closely around the cobalt dimers, with no significant anion–anion interactions, and solvent molecules filling small pockets between anions. Each cation is encapsulated by six nearest neighbour [BPh₄]^- anions, three surrounding each cyclam moiety of the dimer. This close packing results in two C—H···π contacts per cyclam ring from methylene H atoms to the phenyl rings of the anions (Fig. 2). Tetraphenylborate anions have been shown to be better aromatic hydrogen-bond acceptors than phenyl rings in neutral compounds (Steiner et al., 2001), with aromatic hydrogen bonds having typical X···Ph_centroid separations in the range 3.2—3.6 Å (where X is the donor atom). The donor atoms from the cyclam ring are C7—H7A and C9—H9B, with C···Ph_centroid separations of 3.427 (3) and 3.471 (3) Å, respectively. The C—H···Ph_centroid angles are near linear, with H···Ph_centroid distances of 2.614 (3) [H(7 A)] and 2.669 (3) Å [H(9B)].

S2. Experimental

Cyclam was prepared according to published methods (Barefield et al., 1976). CoCl₂ and NaBPh₄ were purchased from Aldrich and used as received. Under a nitrogen atmosphere, a solution of cyclam (75 mg, 0.37 mmol) in EtOH (5 ml) was added to a blue solution of CoCl₂ (50 mg, 0.37 mmol) in EtOH (20 ml). Addition of a solution of NaBPh₄ (253 mg, 0.74 mmol) in EtOH (10 ml) gave an immediate brown precipitate, which analysed as [Co(cyclam)Cl₂](BPh₄)₂ (found: C 72.5, H 6.4, N 6.0%; calculated: C 72.2, H 6.3, N 5.8%), which was collected by filtration, washed with EtOH and Et₂O and dried. Orange–brown crystals suitable for X-ray analysis were grown by allowing the vapour of diethyl ether to diffuse into a concentrated acetone solution (in air) over a period of 3 d.

S3. Refinement

All H atoms were placed in idealized positions and were refined using a riding model (C—H = 0.93–0.98 Å). The anisotropic displacement parameters of the solvent O2 atom are large, suggesting that the atom is disordered over two sites. However, as attempts to model the disorder required severe constraints to yield very little improvement in the structure, this minor artefact was discounted. A view of the body centred array of cation dimers has been deposited.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT and SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2001).

Figures

	Fig. 1. Displacement ellipsoid plot showing the atomic numbering scheme of (I) with atoms represented at the 50% probability level. The acetone molecule has been omitted for clarity.
	Fig. 2. The cobalt dimer forms four interionic C—H···π contacts (shown as dotted lines) to closely packing anions.

µ₂-Peroxo-bis[trans-chloro(1,4,8,11-tetraazacyclotetradecane)cobalt(III)] bis(tetraphenylborate) diacetone solvate

Crystal data

[Co2Cl2(O2)(C10H24N4)2](C24H20B)2·2C3H6O	F(000) = 1444
Mr = 1374.36	Dx = 1.299 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.293 (2) Å	Cell parameters from 2759 reflections
b = 12.5644 (13) Å	θ = 2.4–26.2°
c = 18.225 (2) Å	µ = 0.61 mm^−1
β = 92.610 (2)°	T = 150 K
V = 3498.2 (6) Å^3	Cube, orange-brown
Z = 2	0.24 × 0.22 × 0.16 mm

Data collection

Bruker SMART1000 CCD area-detector diffractometer	8132 independent reflections
Radiation source: fine-focus sealed tube	5620 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 28.6°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −19→19
Tmin = 0.895, Tmax = 1.000	k = −16→16
24509 measured reflections	l = −23→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.059P)^2 + 3.2407P] where P = (Fo^2 + 2Fc^2)/3
8132 reflections	(Δ/σ)max = 0.002
417 parameters	Δρmax = 0.76 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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.

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.

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

	x	y	z	Uiso*/Ueq
Co1	0.97649 (2)	0.04665 (3)	0.880995 (19)	0.02469 (11)
Cl1	0.98379 (5)	0.08026 (6)	0.75935 (4)	0.04120 (19)
B1	1.04066 (19)	−0.4909 (2)	0.74273 (17)	0.0287 (6)
N1	0.91154 (15)	0.18173 (18)	0.89047 (13)	0.0331 (5)
N2	1.08210 (14)	0.13019 (17)	0.90726 (12)	0.0296 (5)
N3	1.04224 (14)	−0.08691 (17)	0.87536 (13)	0.0289 (5)
N4	0.87055 (14)	−0.03848 (19)	0.85657 (13)	0.0333 (5)
O1	0.95899 (10)	0.01988 (14)	0.98155 (10)	0.0268 (4)
O2	0.7523 (2)	−0.7674 (3)	0.5397 (3)	0.1302 (18)
C1	0.78881 (18)	−0.0139 (3)	0.89333 (17)	0.0392 (7)
H1A	0.7963	−0.0326	0.9460	0.047*
H1B	0.7408	−0.0583	0.8715	0.047*
C2	0.76328 (18)	0.1029 (3)	0.88639 (17)	0.0422 (7)
H2A	0.7584	0.1217	0.8336	0.051*
H2B	0.7047	0.1124	0.9065	0.051*
C3	0.82544 (18)	0.1787 (2)	0.92451 (17)	0.0381 (7)
H3A	0.7996	0.2510	0.9231	0.046*
H3B	0.8340	0.1575	0.9767	0.046*
C4	0.97027 (19)	0.2605 (2)	0.92750 (18)	0.0397 (7)
H4A	0.9709	0.2501	0.9814	0.048*
H4B	0.9495	0.3335	0.9162	0.048*
C5	1.0606 (2)	0.2450 (2)	0.90034 (18)	0.0402 (7)
H5B	1.0625	0.2677	0.8484	0.048*
H5A	1.1034	0.2880	0.9300	0.048*
C6	1.16450 (17)	0.1071 (2)	0.86956 (16)	0.0344 (6)
H6B	1.2118	0.1539	0.8897	0.041*
H6A	1.1557	0.1227	0.8165	0.041*
C7	1.19132 (17)	−0.0076 (2)	0.87969 (16)	0.0340 (6)
H7A	1.2502	−0.0172	0.8603	0.041*
H7B	1.1957	−0.0236	0.9329	0.041*
C8	1.12978 (18)	−0.0861 (2)	0.84261 (16)	0.0345 (6)
H8B	1.1225	−0.0682	0.7898	0.041*
H8A	1.1557	−0.1582	0.8466	0.041*
C9	0.98512 (18)	−0.1680 (2)	0.83937 (17)	0.0373 (7)
H9A	1.0066	−0.2402	0.8523	0.045*
H9B	0.9852	−0.1599	0.7853	0.045*
C10	0.89457 (19)	−0.1530 (2)	0.86526 (17)	0.0399 (7)
H10B	0.8528	−0.1979	0.8360	0.048*
H10A	0.8923	−0.1742	0.9175	0.048*
C11	0.94020 (18)	−0.5318 (2)	0.75750 (16)	0.0326 (6)
C12	0.90944 (18)	−0.6329 (2)	0.73724 (16)	0.0341 (6)
H12A	0.9469	−0.6790	0.7118	0.041*
C13	0.82589 (19)	−0.6688 (3)	0.75289 (18)	0.0444 (8)
H13A	0.8075	−0.7378	0.7375	0.053*
C16	0.8801 (2)	−0.4686 (3)	0.79459 (18)	0.0438 (8)
H16A	0.8969	−0.3986	0.8090	0.053*
C17	1.08339 (16)	−0.5720 (2)	0.68290 (15)	0.0295 (6)
C18	1.06889 (17)	−0.5580 (2)	0.60753 (16)	0.0349 (6)
H18A	1.0363	−0.4976	0.5908	0.042*
C19	1.09974 (19)	−0.6281 (3)	0.55552 (17)	0.0414 (7)
H19A	1.0882	−0.6150	0.5047	0.050*
C20	1.14736 (19)	−0.7168 (3)	0.57818 (18)	0.0425 (7)
H20A	1.1689	−0.7651	0.5432	0.051*
C21	1.1631 (2)	−0.7338 (2)	0.65217 (18)	0.0419 (7)
H21A	1.1957	−0.7943	0.6685	0.050*
C22	1.13138 (18)	−0.6629 (2)	0.70314 (17)	0.0354 (6)
H22A	1.1428	−0.6768	0.7539	0.042*
C23	1.09971 (19)	−0.4882 (2)	0.82082 (15)	0.0309 (6)
C24	1.0638 (2)	−0.4779 (2)	0.88990 (17)	0.0384 (7)
H24A	1.0019	−0.4735	0.8921	0.046*
C25	1.1139 (3)	−0.4738 (3)	0.95516 (18)	0.0489 (8)
H25A	1.0860	−0.4675	1.0005	0.059*
C26	1.2036 (3)	−0.4789 (3)	0.95475 (18)	0.0498 (9)
H26A	1.2381	−0.4764	0.9994	0.060*
C27	1.2427 (2)	−0.4877 (2)	0.88813 (18)	0.0426 (7)
H27A	1.3047	−0.4901	0.8867	0.051*
C28	1.19177 (19)	−0.4931 (2)	0.82355 (16)	0.0349 (6)
H28A	1.2204	−0.5004	0.7787	0.042*
C29	1.03965 (17)	−0.3707 (2)	0.70656 (14)	0.0290 (6)
C30	0.96583 (18)	−0.3256 (2)	0.67023 (16)	0.0355 (6)
H30A	0.9126	−0.3646	0.6688	0.043*
C41	0.7700 (2)	−0.6054 (3)	0.79032 (19)	0.0513 (9)
H41A	0.7137	−0.6304	0.8018	0.062*
C31	0.9667 (2)	−0.2269 (3)	0.63622 (16)	0.0399 (7)
H31A	0.9147	−0.1994	0.6128	0.048*
C32	1.0433 (2)	−0.1684 (2)	0.63646 (16)	0.0397 (7)
H32A	1.0444	−0.1005	0.6136	0.048*
C42	0.7975 (2)	−0.5044 (3)	0.8110 (2)	0.0554 (9)
H42B	0.7594	−0.4593	0.8365	0.066*
C33	1.11803 (19)	−0.2101 (2)	0.67028 (16)	0.0360 (6)
H33A	1.1713	−0.1712	0.6703	0.043*
C34	1.11564 (17)	−0.3088 (2)	0.70445 (15)	0.0307 (6)
H34A	1.1681	−0.3356	0.7275	0.037*
C70	0.8926 (4)	−0.8428 (4)	0.5648 (3)	0.0905 (16)
H70A	0.8597	−0.9069	0.5769	0.136*
H70B	0.9260	−0.8178	0.6086	0.136*
H70C	0.9329	−0.8595	0.5261	0.136*
C71	0.8307 (3)	−0.7583 (4)	0.5386 (2)	0.0748 (14)
C72	0.8703 (2)	−0.6596 (3)	0.5098 (2)	0.0585 (10)
H72A	0.8240	−0.6137	0.4885	0.088*
H72B	0.9112	−0.6781	0.4719	0.088*
H72C	0.9018	−0.6220	0.5500	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02234 (18)	0.02999 (19)	0.02203 (19)	0.00174 (14)	0.00420 (13)	0.00147 (15)
Cl1	0.0443 (4)	0.0510 (4)	0.0289 (4)	0.0050 (3)	0.0078 (3)	0.0057 (3)
B1	0.0251 (15)	0.0318 (15)	0.0299 (16)	−0.0015 (12)	0.0076 (12)	−0.0011 (13)
N1	0.0299 (12)	0.0354 (13)	0.0346 (13)	0.0049 (10)	0.0066 (10)	0.0029 (10)
N2	0.0264 (11)	0.0305 (12)	0.0323 (13)	−0.0001 (9)	0.0067 (9)	−0.0012 (10)
N3	0.0259 (11)	0.0282 (11)	0.0329 (13)	0.0009 (9)	0.0051 (9)	−0.0035 (9)
N4	0.0242 (11)	0.0432 (13)	0.0325 (13)	−0.0010 (10)	0.0022 (9)	−0.0012 (11)
O1	0.0178 (8)	0.0370 (10)	0.0257 (9)	0.0050 (7)	0.0022 (7)	0.0022 (8)
O2	0.073 (2)	0.129 (3)	0.196 (4)	−0.049 (2)	0.073 (3)	−0.092 (3)
C1	0.0267 (14)	0.0564 (19)	0.0346 (16)	−0.0043 (13)	0.0014 (12)	−0.0044 (14)
C2	0.0252 (14)	0.065 (2)	0.0365 (17)	0.0106 (14)	0.0047 (12)	0.0062 (15)
C3	0.0321 (15)	0.0442 (17)	0.0383 (17)	0.0137 (13)	0.0066 (12)	0.0059 (13)
C4	0.0442 (17)	0.0301 (15)	0.0454 (18)	0.0046 (12)	0.0096 (14)	−0.0005 (13)
C5	0.0432 (17)	0.0287 (15)	0.0495 (19)	−0.0032 (12)	0.0107 (14)	0.0029 (13)
C6	0.0268 (14)	0.0443 (17)	0.0329 (16)	−0.0044 (12)	0.0101 (11)	0.0019 (13)
C7	0.0242 (13)	0.0473 (16)	0.0313 (15)	0.0039 (12)	0.0094 (11)	−0.0002 (13)
C8	0.0298 (14)	0.0416 (16)	0.0326 (16)	0.0064 (12)	0.0083 (12)	−0.0059 (12)
C9	0.0388 (16)	0.0325 (15)	0.0406 (17)	−0.0009 (12)	0.0012 (13)	−0.0067 (13)
C10	0.0409 (17)	0.0397 (16)	0.0394 (17)	−0.0081 (13)	0.0034 (13)	−0.0079 (13)
C11	0.0279 (14)	0.0398 (16)	0.0306 (15)	0.0001 (11)	0.0070 (11)	0.0046 (12)
C12	0.0278 (14)	0.0417 (16)	0.0328 (15)	−0.0043 (12)	0.0019 (11)	0.0104 (13)
C13	0.0321 (16)	0.0559 (19)	0.0447 (19)	−0.0099 (14)	−0.0031 (13)	0.0227 (15)
C16	0.0350 (16)	0.0486 (19)	0.049 (2)	0.0066 (13)	0.0179 (14)	0.0044 (15)
C17	0.0218 (12)	0.0324 (14)	0.0348 (15)	−0.0050 (10)	0.0073 (11)	−0.0034 (11)
C18	0.0255 (14)	0.0450 (17)	0.0343 (16)	−0.0006 (12)	0.0030 (11)	−0.0058 (13)
C19	0.0318 (15)	0.060 (2)	0.0325 (16)	−0.0012 (14)	0.0039 (12)	−0.0119 (14)
C20	0.0358 (16)	0.0480 (18)	0.0447 (19)	−0.0025 (13)	0.0121 (13)	−0.0167 (15)
C21	0.0395 (17)	0.0344 (16)	0.053 (2)	0.0001 (13)	0.0126 (14)	−0.0055 (14)
C22	0.0366 (15)	0.0346 (15)	0.0360 (16)	−0.0037 (12)	0.0115 (12)	−0.0005 (12)
C23	0.0389 (15)	0.0246 (13)	0.0298 (15)	−0.0001 (11)	0.0074 (12)	−0.0003 (11)
C24	0.0474 (18)	0.0312 (15)	0.0376 (17)	−0.0029 (12)	0.0135 (14)	−0.0054 (12)
C25	0.075 (3)	0.0410 (18)	0.0309 (17)	−0.0047 (16)	0.0103 (16)	−0.0051 (13)
C26	0.077 (3)	0.0386 (18)	0.0327 (17)	0.0010 (16)	−0.0127 (16)	−0.0048 (13)
C27	0.0454 (18)	0.0362 (16)	0.0453 (19)	0.0052 (13)	−0.0067 (14)	−0.0013 (14)
C28	0.0371 (15)	0.0351 (15)	0.0327 (15)	0.0045 (12)	0.0033 (12)	0.0006 (12)
C29	0.0289 (13)	0.0338 (14)	0.0249 (13)	−0.0018 (11)	0.0072 (11)	−0.0045 (11)
C30	0.0302 (14)	0.0424 (16)	0.0342 (16)	−0.0033 (12)	0.0031 (12)	−0.0014 (13)
C41	0.0263 (15)	0.074 (2)	0.054 (2)	−0.0049 (15)	0.0077 (14)	0.0292 (18)
C31	0.0390 (16)	0.0467 (17)	0.0337 (17)	0.0085 (13)	−0.0009 (13)	0.0029 (13)
C32	0.0509 (18)	0.0362 (16)	0.0325 (16)	0.0004 (13)	0.0075 (13)	0.0032 (13)
C42	0.0367 (18)	0.076 (2)	0.055 (2)	0.0154 (17)	0.0214 (16)	0.0173 (19)
C33	0.0385 (16)	0.0368 (15)	0.0334 (16)	−0.0070 (12)	0.0079 (12)	−0.0008 (12)
C34	0.0286 (14)	0.0336 (14)	0.0303 (15)	−0.0020 (11)	0.0043 (11)	−0.0011 (11)
C70	0.123 (4)	0.093 (4)	0.056 (3)	−0.028 (3)	0.022 (3)	0.004 (3)
C71	0.061 (3)	0.098 (3)	0.067 (3)	−0.026 (2)	0.030 (2)	−0.044 (3)
C72	0.0394 (19)	0.087 (3)	0.049 (2)	−0.0069 (18)	0.0079 (16)	−0.012 (2)

Geometric parameters (Å, º)

Co1—O1	1.8943 (18)	C11—C12	1.399 (4)
Co1—N1	1.978 (2)	C11—C16	1.410 (4)
Co1—N2	1.967 (2)	C12—C13	1.396 (4)
Co1—N3	1.961 (2)	C13—C41	1.372 (5)
Co1—N4	1.975 (2)	C16—C42	1.386 (4)
Co1—Cl1	2.2647 (8)	C17—C18	1.393 (4)
B1—C11	1.654 (4)	C17—C22	1.398 (4)
B1—C17	1.649 (4)	C18—C19	1.392 (4)
B1—C23	1.651 (4)	C19—C20	1.384 (5)
B1—C29	1.647 (4)	C20—C21	1.376 (5)
N1—C4	1.478 (4)	C21—C22	1.390 (4)
N1—C3	1.481 (3)	C23—C24	1.402 (4)
N2—C5	1.484 (4)	C23—C28	1.408 (4)
N2—C6	1.491 (3)	C24—C25	1.387 (5)
N3—C9	1.476 (3)	C25—C26	1.374 (5)
N3—C8	1.490 (3)	C26—C27	1.382 (5)
N4—C1	1.477 (4)	C27—C28	1.384 (4)
N4—C10	1.492 (4)	C29—C34	1.400 (4)
O1—O1^i	1.483 (3)	C29—C30	1.402 (4)
O2—C71	1.206 (5)	C30—C31	1.387 (4)
C1—C2	1.523 (5)	C41—C42	1.383 (5)
C2—C3	1.495 (4)	C31—C32	1.383 (4)
C4—C5	1.501 (4)	C32—C33	1.376 (4)
C6—C7	1.507 (4)	C33—C34	1.390 (4)
C7—C8	1.503 (4)	C70—C71	1.486 (7)
C9—C10	1.495 (4)	C71—C72	1.486 (6)
O1—Co1—N3	89.66 (8)	C8—C7—C6	114.3 (2)
O1—Co1—N2	90.57 (8)	N3—C8—C7	112.3 (2)
N3—Co1—N2	92.99 (9)	N3—C9—C10	108.1 (2)
O1—Co1—N4	88.36 (9)	N4—C10—C9	108.4 (2)
N3—Co1—N4	86.68 (9)	C12—C11—C16	114.8 (3)
N2—Co1—N4	178.87 (10)	C12—C11—B1	122.9 (2)
O1—Co1—N1	88.52 (9)	C16—C11—B1	122.3 (3)
N3—Co1—N1	177.93 (10)	C13—C12—C11	122.6 (3)
N2—Co1—N1	86.04 (9)	C41—C13—C12	120.7 (3)
N4—Co1—N1	94.26 (10)	C42—C16—C11	122.8 (3)
O1—Co1—Cl1	174.69 (5)	C18—C17—C22	114.9 (3)
N3—Co1—Cl1	93.44 (7)	C18—C17—B1	121.6 (2)
N2—Co1—Cl1	93.57 (7)	C22—C17—B1	123.3 (3)
N4—Co1—Cl1	87.52 (7)	C19—C18—C17	123.3 (3)
N1—Co1—Cl1	88.45 (7)	C20—C19—C18	119.8 (3)
C29—B1—C17	107.4 (2)	C21—C20—C19	118.9 (3)
C29—B1—C23	108.7 (2)	C20—C21—C22	120.3 (3)
C17—B1—C23	111.4 (2)	C21—C22—C17	122.8 (3)
C29—B1—C11	111.0 (2)	C24—C23—C28	113.9 (3)
C17—B1—C11	108.3 (2)	C24—C23—B1	123.7 (3)
C23—B1—C11	110.0 (2)	C28—C23—B1	122.4 (2)
C4—N1—C3	111.0 (2)	C25—C24—C23	123.3 (3)
C4—N1—Co1	108.48 (17)	C26—C25—C24	120.5 (3)
C3—N1—Co1	118.31 (18)	C25—C26—C27	118.7 (3)
C5—N2—C6	109.8 (2)	C26—C27—C28	120.1 (3)
C5—N2—Co1	108.77 (17)	C27—C28—C23	123.5 (3)
C6—N2—Co1	119.07 (17)	C34—C29—C30	114.5 (3)
C9—N3—C8	110.5 (2)	C34—C29—B1	121.8 (2)
C9—N3—Co1	108.63 (16)	C30—C29—B1	123.5 (2)
C8—N3—Co1	119.16 (17)	C31—C30—C29	123.3 (3)
C1—N4—C10	111.3 (2)	C13—C41—C42	118.7 (3)
C1—N4—Co1	119.14 (18)	C32—C31—C30	119.9 (3)
C10—N4—Co1	107.63 (17)	C33—C32—C31	119.0 (3)
O1^i—O1—Co1	110.17 (16)	C41—C42—C16	120.5 (3)
N4—C1—C2	112.5 (2)	C32—C33—C34	120.1 (3)
C3—C2—C1	114.9 (2)	C33—C34—C29	123.2 (3)
N1—C3—C2	112.3 (2)	O2—C71—C70	123.1 (5)
N1—C4—C5	108.2 (2)	O2—C71—C72	120.4 (5)
N2—C5—C4	107.5 (2)	C70—C71—C72	116.5 (4)
N2—C6—C7	111.1 (2)

Symmetry code: (i) −x+2, −y, −z+2.