A novel cobalt(II) coordination polymer with an unusual four-connected 4².6³.8 topology

In the cobalt(II) coordination polymer poly[[(μ₂-benzene-1,3-dicarboxyl­ato){μ₂-1,1′-[2,2′-oxybis(ethane-2,1-di­yl)]di-1H-imidazole}cobalt(II)] monohydrate], {[Co(C₁₀H₁₄N₄O)(C₈H₄O₄)]·H₂O}_n, two crystallographically distinct Co^II cations are four-coordinated by N₂O₂ donor sets in distorted tetra­hedral geometries. The Co^II centers are connected by benzene-1,3-dicarboxyl­ate (m-BDC) anions, giving two types of linear chains, which are further joined via meso-helical 1,1′-[2,2′-oxybis(ethane-2,1-di­yl)]di-1H-imidazole ligands to yield a thick two-dimensional slab. The compound displays a two-dimensional four-connected 4².6³.8 topology, which is unprecedented in coordination polymers.

S1. Comment

The design and synthesis of metal–organic coordination polymers are of great interest, not only because of their tremendous potential applications in nonlinear optics, catalysis, gas absorption, luminescence, magnetism and medicine, but also because of their intriguing variety of architectures and topologies (Wu et al., 2005; Spencer et al., 2006). The construction of coordination networks with different topological characteristics has attracted significant attention among chemists. By judicious choice of the organic spacers and the central metals, it is possible to produce different types of coordination networks with novel topologies. So far, numerous fascinating archetypal topological structures, including diamond (6⁶), SrSi₂ (10³-a), α-ThSi₂ (10³-b), SiO₂ (6⁴8²-b), and PtS (4².8⁴), have provided experimental examples of these theoretical topologies. In this regard, 4-connected networks are particularly interesting (Zhang et al., 2005; Abrahams et al., 1999; Carlucci et al., 2002). The majority of 4-connected nets are constructed by tetrahedral or square-planar nodes. Typical 4-connected nets such as 6⁶, 6⁴.8², 4².8⁴ and 7⁵.9 have been documented (Wells, 1984; Bregeaul & Herpin, 1970; Hawkins et al., 1993; Qi et al., 2008; Long et al., 2004; Fang et al., 2008; Bhogala et al., 2004; Carlucci et al., 1998).

We have reported several 4-connected structures, such as the first square-planar four-connected 8⁶ net made using the flexible 1,1'-(1,4-butanediyl)bis(imidazole) ligand (Ma et al., 2003, 2004; Yang et al., 2005, 2006). In order to extend the study on topologies of coordination polymers with flexible ligands, a new flexible bis(imidazole) ligand, 1,1'-[2,2'-oxybis(ethane-2,1-diyl)]di-1H-imidazole (L), was used (Wei et al., 2008). L, as a secondary N-donor bridging ligand, contains a heteroatom, oxygen, at the symmetric center of the molecule. Therefore, the two imidazole rings can twist freely around the –O– group to meet the requirements of the coordination geometries of metal atoms in the assembly process. Furthermore, owing to the presence of the flexible –CH₂– spacer, the L ligand can exhibit more flexible conformations. In this contribution, L and m-BDC (m-BDC is deprotonated m-benzenedicarboxylic acid) were used as bridging ligands, and a new cobalt(II) coordination polymer, namely {[Co(C₁₀H₁₄N₄O)(C₈H₄O₄)].H₂O}_n, (I), was obtained under hydrothermal conditions. Compound (I) is a rare example of a two-dimensional structure with a unique 4².6³.8 topology based solely upon tetrahedral nodes.

The asymmetric unit of (I) contains two crystallographically distinct Co^II cations (Fig. 1), two unique m-BDC anions and two unique L ligands. Each Co^II ion has a distorted tetrahedral coordination environment formed by two carboxylate O atoms from two m-BDC anions [Co—O = 1.970 (3)–2.018 (3) Å] and two N atoms from two L ligands [Co—N = 2.018 (3)–2.035 (3) Å]. Each m-BDC anion coordinates two Co^II centers in a bis-monodentate mode (see scheme; the Co···Co distances through m-BDC are both 10.041 (1) Å, because both correspond to C-lattice translations. The two cobalt(II) cations are bridged by the crystallographically independent m-BDC anions to form two independent one-dimensional Co–m-BDC chains (Fig. 2). The Co2···Co2^vi chain propagates along [110] [symmetry code: (vi) x + 1/2, y + 1/2, z] in the plane z = 0.127, while the Co1···Co1^v chain propagates parallel to [110] [symmetry code: (v) x + 1/2, y - 1/2, z] in the plane z = 0.393. That is, the chains that run vertically in Fig. 2 are at a different elevation from those that run horizontally. The propagation vectors of the two Co–m-BDC polymer chains are at 81.93 (5)° to each other (Fig. 2). The two crystallographically distinct L ligands exhibit similar conformations, which link atoms Co1 and Co2 to generate an interesting meso-helical chain (Han & Hong, 2005), with Co1···Co2 distances of 8.211 (3) and Co1···Co2^iv distances of 10.729 (5) Å [symmetry code: (iv) x + 1, y, z; Figs. 3 and 4]. The two imidazole rings of each L ligand are far from parallel [having dihedral angles of 81.1 (3)° between the N1- and N3-containg rings, 70.4 (4)° between the N5 and N7 rings, 79.3 (3)° between the N1 and N5 rings, and 87.3 (3)° between the N7 and N3ⁱⁱⁱ rings; symmetry code: (iii) x - 1, y, z; Fig. 3]. Obviously, these twists are important factors in forming the helical structure. The two independent L ligands link the nearly perpendicular Co–m-BDC chains into a slab (Fig. 5). Furthermore, these linear chains are connected by hydrogen bonding bridged by uncoordinated water molecules, which enhance the stability of the two-dimensional network. The adjacent two-dimensional slabs are stacked in a staggered pattern (–ABAB– sequence) along the c axis.

Better insight into the structure of (I) can be achieved by application of topological concepts, describing the multidimensional structure in terms of simple node-and-linker nets. The Co^II center is described as a tetrahedral 4-connected node. The m-BDC and L ligands are bridges. With reference to Fig. 4, the Co1ⁱ···Co1···Co1^v angle with links formed by the m-BDC ligand is 180° and the Co2···Co1···Co2^iv dihedral angle with links formed by the flexible L ligand is 81.93 (5)° [symmetry code: (i) x - 1/2, y + 1/2, z]. From a topological perspective, the resulting structure of (I) is a uninodal 4-connected two-dimensional net with the short (Schläfli) vertex symbol 4².6³.8 and with the long-form circuit symbol 4.4.6₂.6₂.6₄.8 (Fig. 5) (Treacy et al., 2006; OLEX; Dolomanov et al., 2003). The topology of a single frame can be rationalized by considering that the shortest circuits starting and ending at each cobalt(II) cation are tetragons, hexagons and octagons in the ratio 2:3:1; that is, this is a 4².6³.8-net (Wells, 1979).

It is noteworthy that the 4².6³.8-net presented here is clearly different from the two-dimensional 4-connected (4,4)-networks that have been widely reported. We are not aware of any previously reported coordination polymer with a two-dimensional 4-connected structure with this topology. Polymer (I) appears to be the first example of a two-dimensional 4-connected net with 4².6³.8 topology. The flexibility of the ligand L may play an important role in the formation of this unusual structure.

Related literature

For related literature, see: Abrahams et al. (1999); Bhogala et al. (2004); Bregeaul & Herpin (1970); Carlucci et al. (1998, 2002); Dolomanov et al. (2003); Fang et al. (2008); Han & Hong (2005); Hawkins et al. (1993); Long et al. (2004); Ma et al. (2003, 2004); Qi et al. (2008); Spencer et al. (2006); Wei et al. (2008); Wells (1979, 1984); Wu et al. (2005); Yang et al. (2005, 2006); Zhang et al. (2005).

S2. Experimental

A mixture of Co(NO₃)₂.6H₂O (29.1 mg, 0.10 mmol), m-H₂BDC (16.7 mg, 0.10 mmol), L (20.6 mg, 0.10 mmol) and water (7 ml) was sealed in a Teflon reactor (15 ml), which was heated at 453 K for 3 d and then cooled gradually to room temperature. Purple crystals of (I) were isolated using a cobalt(II)/L/m-H₂BDC molar ratio of 1:1:1 (yield 84% based on Co). Analysis calculated for C₃₆H₄₀Co₂N₈O₁₂ (M_r = 894.62): C 48.33, H 4.50, N 12.53%; found: C 48.34, H 4.50, N 12.52%. IR (cm^-1, KBr): 3110 (s), 3047 (s), 2915 (vs), 1605 (vs), 1391 (s), 1347 (s), 1106 (s), 753 (s), 656 (s).

S3. Refinement

H atoms bonded to C atoms were positioned geometrically (C—H = 0.93 and 0.97 Å) and refined as riding, with U_iso(H) values of 1.2U_eq(C). The water H-atoms were located in a difference Fourier map and were refined with O—H distance restraints of 0.85 (please provide s.u. value) Å; their displacement parameters were tied to those of parent atoms by a factor of 1.2 [not true according to CIF; they have a common value of 0.167 Ų].

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The local coordination of the Co^II cations in (I), showing the atom-numbering scheme. Displacement ellipsoids are shown at the 30% probability level. [Symmetry codes: (i) x - 1/2, y + 1/2, z; (ii) x - 1/2, y - 1/2, z; (iii) x - 1, y, z.]
	Fig. 2. The perpendicular linear Co–m-BDC chains.
	Fig. 3. Infinite meso-helical chain formed by two types of L ligands.
	Fig. 4. A schematic illustation of the distances and angles between topological nodes [Co1···Co1^i = 10.041 (1) Å, Co1···Co2 = 10.730 (1) Å, Co1···Co2^iv = 8.211 (1) Å, Co1^i—Co1—Co2 = 123.35 (4)°, Co2—Co1—Co1^v = 56.65 (3)°, Co1^v—Co1—Co2^iv = 132.55 (5)° and Co2^iv—Co1—Co1^i = 47.45 (3)°] and two types of angles between adjacent nodes [Co2···Co1··· Co2^iv = 81.93 (5)° and Co1^i···Co1···Co1^v = 180°] in (I). [Symmetry codes: (i) x - 1/2, y + 1/2, z; (iv) x + 1, y, z; (v) x + 1/2, y - 1/2, z.]
	Fig. 5. A schematic representation of the slab and highlighted representation of the 4^2.6^3.8 topology of the two-dimensional 4-connected network. [Symmetry codes: (i) x - 1/2, y + 1/2, z; (ii) x - 1/2, y - 1/2, z; (iii) x - 1, y, z; (iv) x + 1, y, z; (v) x + 1/2, y - 1/2, z; (vi) x + 1/2, y + 1/2, z.] Table 2 iv -> v and v -> vii

poly[[(µ₂-benzene-1,3-dicarboxylato){µ₂-1,1'-[2,2'-oxybis(ethane-2,1- diyl)]di-1H-imidazole}cobalt(II)] monohydrate]

Crystal data

[Co(C10H14N4O)(C8H4O4)]·H2O	F(000) = 1848
Mr = 447.31	Dx = 1.476 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: C -2yc	Cell parameters from 4840 reflections
a = 15.1641 (9) Å	θ = 2–25°
b = 13.1653 (9) Å	µ = 0.90 mm^−1
c = 20.6761 (19) Å	T = 293 K
β = 102.753 (1)°	Block, purple
V = 4025.9 (5) Å^3	0.44 × 0.32 × 0.19 mm
Z = 8

Data collection

Bruker APEX CCD area-detector diffractometer	5554 independent reflections
Radiation source: fine-focus sealed tube	4840 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→18
Tmin = 0.711, Tmax = 0.841	k = −13→15
10068 measured reflections	l = −24→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0402P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
5554 reflections	Δρmax = 0.46 e Å^−3
535 parameters	Δρmin = −0.27 e Å^−3
4 restraints	Absolute structure: Flack (1983), 1999 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.007 (12)

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	0.59672 (3)	1.07560 (4)	0.12677 (3)	0.03690 (14)
Co2	0.28068 (3)	1.19311 (4)	0.39342 (3)	0.03903 (15)
C1	0.7174 (3)	1.1442 (3)	0.2550 (2)	0.0417 (9)
H1	0.7666	1.1099	0.2456	0.050*
C2	0.5844 (3)	1.2016 (3)	0.2496 (2)	0.0519 (11)
H2	0.5229	1.2139	0.2349	0.062*
C3	0.6374 (3)	1.2411 (4)	0.3047 (2)	0.0536 (12)
H3	0.6196	1.2850	0.3347	0.064*
C4	0.8036 (3)	1.2323 (4)	0.3573 (2)	0.0593 (13)
H4A	0.8515	1.1843	0.3555	0.071*
H4B	0.7915	1.2296	0.4015	0.071*
C5	0.8328 (3)	1.3369 (4)	0.3437 (3)	0.0627 (13)
H5A	0.8428	1.3410	0.2990	0.075*
H5B	0.7868	1.3859	0.3481	0.075*
C6	0.9403 (3)	1.4604 (4)	0.3907 (3)	0.0585 (12)
H6A	0.8959	1.5031	0.4049	0.070*
H6B	0.9444	1.4810	0.3465	0.070*
C7	1.0296 (3)	1.4717 (4)	0.4371 (2)	0.0542 (12)
H7A	1.0418	1.5433	0.4458	0.065*
H7B	1.0275	1.4392	0.4789	0.065*
C8	1.1422 (3)	1.4674 (4)	0.3632 (3)	0.0647 (14)
H8	1.1280	1.5289	0.3411	0.078*
C9	1.2045 (3)	1.4013 (4)	0.3539 (3)	0.0600 (13)
H9	1.2421	1.4094	0.3243	0.072*
C10	1.1420 (3)	1.3389 (3)	0.4281 (2)	0.0416 (10)
H10	1.1272	1.2954	0.4595	0.050*
C11	0.4490 (3)	0.9192 (3)	0.0960 (2)	0.0476 (11)
H11	0.4141	0.9599	0.0633	0.057*
C12	0.5569 (4)	0.8647 (4)	0.1723 (3)	0.0825 (19)
H12	0.6118	0.8597	0.2029	0.099*
C13	0.4893 (4)	0.7956 (4)	0.1626 (3)	0.090 (2)
H13	0.4892	0.7348	0.1854	0.108*
C14	0.3368 (3)	0.7799 (4)	0.0858 (3)	0.0692 (15)
H14A	0.3134	0.8065	0.0416	0.083*
H14B	0.3480	0.7079	0.0817	0.083*
C15	0.2691 (5)	0.7927 (5)	0.1245 (4)	0.099 (2)
H15A	0.2167	0.7518	0.1050	0.119*
H15B	0.2930	0.7670	0.1689	0.119*
C16	0.1631 (4)	0.9020 (5)	0.1544 (3)	0.090 (2)
H16A	0.1736	0.8744	0.1989	0.108*
H16B	0.1135	0.8650	0.1267	0.108*
C17	0.1405 (3)	1.0105 (5)	0.1553 (3)	0.0763 (16)
H17A	0.1382	1.0389	0.1116	0.092*
H17B	0.0807	1.0173	0.1645	0.092*
C18	0.2877 (3)	1.1029 (4)	0.1990 (3)	0.0611 (13)
H18	0.3144	1.0959	0.1628	0.073*
C19	0.3230 (3)	1.1485 (4)	0.2569 (2)	0.0599 (13)
H19	0.3795	1.1795	0.2674	0.072*
C20	0.1928 (3)	1.0941 (4)	0.2641 (2)	0.0536 (12)
H20	0.1413	1.0792	0.2797	0.064*
C21	0.7544 (3)	0.9815 (3)	0.1130 (2)	0.0424 (10)
C22	0.8204 (2)	0.9414 (3)	0.0749 (2)	0.0342 (9)
C23	0.8341 (3)	0.9904 (3)	0.0182 (2)	0.0444 (10)
H23	0.8023	1.0493	0.0034	0.053*
C24	0.8953 (3)	0.9508 (3)	−0.0160 (2)	0.0497 (11)
H24	0.9049	0.9841	−0.0535	0.060*
C25	0.9421 (3)	0.8627 (3)	0.0051 (2)	0.0421 (10)
H25	0.9836	0.8373	−0.0179	0.050*
C26	0.9272 (2)	0.8122 (3)	0.06058 (18)	0.0317 (8)
C27	0.8672 (2)	0.8517 (3)	0.09497 (18)	0.0323 (8)
H27	0.8576	0.8178	0.1323	0.039*
C28	0.9730 (3)	0.7129 (3)	0.0837 (2)	0.0370 (9)
C29	0.4407 (3)	1.2786 (3)	0.4178 (2)	0.0387 (9)
C30	0.5333 (3)	1.3168 (3)	0.44829 (19)	0.0337 (9)
C31	0.5917 (3)	1.2643 (3)	0.4974 (2)	0.0504 (11)
H31	0.5727	1.2043	0.5138	0.061*
C32	0.6783 (3)	1.2999 (4)	0.5228 (3)	0.0610 (13)
H32	0.7177	1.2631	0.5552	0.073*
C33	0.7060 (3)	1.3906 (4)	0.4996 (2)	0.0537 (12)
H33	0.7645	1.4143	0.5161	0.064*
C34	0.6470 (2)	1.4460 (3)	0.4521 (2)	0.0375 (9)
C35	0.5618 (2)	1.4084 (3)	0.42610 (18)	0.0329 (8)
H35	0.5227	1.4447	0.3932	0.039*
C36	0.6734 (3)	1.5474 (3)	0.4277 (2)	0.0413 (10)
N1	0.6354 (2)	1.1400 (2)	0.21813 (16)	0.0384 (8)
N2	0.7214 (2)	1.2043 (3)	0.30794 (16)	0.0456 (9)
N3	1.1026 (2)	1.4277 (2)	0.41162 (19)	0.0434 (8)
N4	1.2045 (2)	1.3194 (2)	0.39478 (17)	0.0413 (8)
N5	0.5302 (2)	0.9434 (3)	0.12895 (18)	0.0472 (9)
N6	0.4225 (3)	0.8306 (3)	0.1144 (2)	0.0561 (10)
N7	0.2045 (3)	1.0689 (3)	0.20420 (19)	0.0559 (10)
N8	0.2640 (2)	1.1430 (3)	0.29847 (16)	0.0449 (8)
O1	0.69757 (19)	1.0482 (2)	0.08332 (15)	0.0491 (7)
O2	0.7561 (2)	0.9512 (3)	0.16961 (16)	0.0619 (9)
O3	0.9419 (2)	0.6577 (2)	0.12121 (17)	0.0592 (9)
O4	1.04582 (18)	0.6901 (2)	0.06551 (14)	0.0433 (7)
O5	0.40953 (18)	1.2043 (2)	0.44555 (15)	0.0479 (7)
O6	0.3958 (2)	1.3188 (2)	0.36714 (16)	0.0577 (9)
O7	0.6159 (2)	1.5991 (2)	0.39070 (17)	0.0617 (9)
O8	0.7556 (2)	1.5744 (2)	0.44611 (16)	0.0536 (8)
O9	0.9138 (2)	1.3568 (2)	0.39055 (16)	0.0611 (9)
O10	0.2414 (3)	0.8919 (4)	0.1291 (3)	0.1064 (16)
O1W	0.9264 (4)	0.9184 (4)	0.2560 (2)	0.0947 (14)
O2W	0.4608 (4)	0.6253 (4)	0.2791 (3)	0.1110 (18)
H1A	0.861 (6)	0.932 (6)	0.236 (4)	0.167*
H1B	0.911 (6)	0.905 (7)	0.291 (3)	0.167*
H2A	0.496 (6)	0.621 (7)	0.317 (4)	0.167*
H2B	0.467 (7)	0.569 (7)	0.260 (5)	0.167*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0374 (3)	0.0295 (3)	0.0439 (3)	0.0036 (2)	0.0093 (2)	−0.0014 (3)
Co2	0.0341 (3)	0.0369 (3)	0.0459 (3)	−0.0058 (3)	0.0084 (2)	−0.0022 (3)
C1	0.042 (2)	0.037 (2)	0.048 (2)	0.0008 (18)	0.014 (2)	−0.0020 (19)
C2	0.043 (3)	0.059 (3)	0.058 (3)	−0.002 (2)	0.022 (2)	−0.010 (2)
C3	0.055 (3)	0.057 (3)	0.053 (3)	0.001 (2)	0.020 (2)	−0.014 (2)
C4	0.059 (3)	0.062 (3)	0.050 (3)	−0.007 (2)	−0.001 (2)	−0.004 (2)
C5	0.054 (3)	0.060 (3)	0.067 (3)	−0.004 (2)	−0.003 (2)	−0.002 (3)
C6	0.056 (3)	0.044 (3)	0.074 (3)	0.004 (2)	0.011 (3)	0.001 (2)
C7	0.057 (3)	0.041 (3)	0.064 (3)	0.002 (2)	0.012 (2)	−0.011 (2)
C8	0.069 (3)	0.046 (3)	0.085 (4)	0.008 (2)	0.031 (3)	0.027 (3)
C9	0.063 (3)	0.058 (3)	0.064 (3)	0.002 (3)	0.025 (2)	0.021 (3)
C10	0.043 (2)	0.027 (2)	0.056 (3)	−0.0025 (18)	0.012 (2)	−0.0004 (19)
C11	0.051 (3)	0.031 (2)	0.059 (3)	0.003 (2)	0.007 (2)	−0.001 (2)
C12	0.078 (4)	0.055 (4)	0.095 (4)	−0.011 (3)	−0.023 (3)	0.032 (3)
C13	0.103 (5)	0.051 (3)	0.102 (5)	−0.019 (3)	−0.008 (4)	0.033 (3)
C14	0.077 (4)	0.047 (3)	0.082 (4)	−0.024 (3)	0.014 (3)	−0.019 (3)
C15	0.105 (5)	0.087 (5)	0.118 (5)	−0.053 (4)	0.053 (5)	−0.039 (4)
C16	0.083 (4)	0.097 (5)	0.093 (5)	−0.045 (4)	0.024 (4)	−0.035 (4)
C17	0.058 (3)	0.108 (5)	0.059 (3)	−0.019 (3)	0.007 (3)	−0.017 (3)
C18	0.064 (3)	0.071 (3)	0.057 (3)	−0.015 (3)	0.031 (2)	−0.014 (3)
C19	0.052 (3)	0.065 (3)	0.067 (3)	−0.016 (2)	0.023 (2)	−0.011 (3)
C20	0.043 (3)	0.071 (3)	0.051 (3)	−0.007 (2)	0.019 (2)	−0.005 (2)
C21	0.036 (2)	0.037 (3)	0.053 (3)	0.0082 (19)	0.008 (2)	−0.006 (2)
C22	0.025 (2)	0.032 (2)	0.044 (2)	0.0039 (16)	0.0056 (17)	−0.0054 (17)
C23	0.046 (2)	0.030 (2)	0.056 (3)	0.0107 (18)	0.009 (2)	0.0076 (19)
C24	0.054 (3)	0.047 (3)	0.054 (3)	0.007 (2)	0.024 (2)	0.011 (2)
C25	0.034 (2)	0.043 (2)	0.051 (2)	0.0073 (18)	0.0151 (19)	−0.002 (2)
C26	0.0256 (19)	0.028 (2)	0.040 (2)	0.0038 (15)	0.0036 (16)	−0.0050 (16)
C27	0.030 (2)	0.026 (2)	0.039 (2)	0.0065 (16)	0.0035 (16)	0.0015 (16)
C28	0.031 (2)	0.031 (2)	0.047 (2)	0.0076 (17)	0.0038 (18)	−0.0031 (18)
C29	0.033 (2)	0.035 (2)	0.048 (2)	−0.0082 (18)	0.0109 (19)	−0.0031 (19)
C30	0.031 (2)	0.030 (2)	0.042 (2)	−0.0057 (16)	0.0113 (17)	−0.0038 (17)
C31	0.047 (3)	0.033 (2)	0.067 (3)	−0.007 (2)	0.002 (2)	0.008 (2)
C32	0.042 (3)	0.046 (3)	0.085 (4)	−0.005 (2)	−0.009 (2)	0.011 (2)
C33	0.031 (2)	0.049 (3)	0.075 (3)	−0.011 (2)	−0.001 (2)	−0.001 (2)
C34	0.033 (2)	0.033 (2)	0.050 (2)	−0.0105 (17)	0.0170 (19)	−0.0064 (18)
C35	0.027 (2)	0.033 (2)	0.040 (2)	−0.0041 (16)	0.0112 (16)	−0.0009 (16)
C36	0.046 (3)	0.038 (2)	0.047 (2)	−0.019 (2)	0.024 (2)	−0.0099 (19)
N1	0.039 (2)	0.035 (2)	0.0416 (19)	0.0011 (15)	0.0096 (16)	−0.0026 (15)
N2	0.049 (2)	0.045 (2)	0.042 (2)	−0.0036 (16)	0.0056 (17)	−0.0067 (16)
N3	0.041 (2)	0.034 (2)	0.054 (2)	−0.0010 (16)	0.0089 (17)	0.0023 (16)
N4	0.039 (2)	0.0343 (19)	0.049 (2)	−0.0026 (15)	0.0068 (17)	−0.0002 (15)
N5	0.048 (2)	0.034 (2)	0.057 (2)	0.0008 (16)	0.0055 (18)	0.0037 (16)
N6	0.065 (3)	0.035 (2)	0.067 (3)	−0.0101 (19)	0.013 (2)	0.0003 (18)
N7	0.051 (2)	0.069 (3)	0.049 (2)	−0.0130 (19)	0.0124 (19)	−0.0097 (19)
N8	0.042 (2)	0.048 (2)	0.047 (2)	−0.0078 (17)	0.0130 (17)	−0.0011 (17)
O1	0.0425 (16)	0.0424 (17)	0.0628 (19)	0.0211 (14)	0.0128 (14)	0.0015 (14)
O2	0.069 (2)	0.066 (2)	0.057 (2)	0.0274 (17)	0.0277 (18)	0.0086 (17)
O3	0.059 (2)	0.0363 (18)	0.088 (2)	0.0135 (15)	0.0284 (18)	0.0141 (17)
O4	0.0358 (16)	0.0413 (16)	0.0516 (17)	0.0147 (12)	0.0070 (13)	−0.0057 (13)
O5	0.0375 (16)	0.0400 (16)	0.0655 (19)	−0.0167 (13)	0.0099 (14)	0.0045 (14)
O6	0.0423 (18)	0.061 (2)	0.061 (2)	−0.0201 (16)	−0.0077 (16)	0.0100 (17)
O7	0.068 (2)	0.0419 (19)	0.075 (2)	−0.0177 (17)	0.0143 (19)	0.0130 (17)
O8	0.0445 (18)	0.0526 (19)	0.068 (2)	−0.0260 (15)	0.0208 (15)	−0.0090 (15)
O9	0.0545 (19)	0.046 (2)	0.072 (2)	−0.0004 (15)	−0.0081 (17)	0.0000 (16)
O10	0.079 (3)	0.085 (3)	0.168 (5)	−0.036 (2)	0.054 (3)	−0.059 (3)
O1W	0.108 (3)	0.105 (3)	0.064 (2)	−0.007 (3)	0.006 (3)	0.018 (2)
O2W	0.092 (4)	0.099 (4)	0.132 (5)	0.005 (3)	0.003 (3)	0.036 (4)

Geometric parameters (Å, º)

Co1—O1	1.970 (3)	C16—C17	1.470 (8)
Co1—O4^i	2.011 (3)	C16—H16A	0.9700
Co1—N5	2.018 (3)	C16—H16B	0.9700
Co1—N1	2.035 (3)	C17—N7	1.458 (6)
Co2—O8^ii	1.989 (3)	C17—H17A	0.9700
Co2—O5	2.018 (3)	C17—H17B	0.9700
Co2—N4^iii	2.029 (3)	C18—C19	1.341 (7)
Co2—N8	2.033 (3)	C18—N7	1.365 (6)
C1—N1	1.308 (5)	C18—H18	0.9300
C1—N2	1.341 (5)	C19—N8	1.373 (5)
C1—H1	0.9300	C19—H19	0.9300
C2—C3	1.346 (6)	C20—N8	1.321 (5)
C2—N1	1.377 (5)	C20—N7	1.331 (6)
C2—H2	0.9300	C20—H20	0.9300
C3—N2	1.351 (5)	C21—O2	1.232 (5)
C3—H3	0.9300	C21—O1	1.287 (5)
C4—N2	1.473 (5)	C21—C22	1.499 (5)
C4—C5	1.492 (7)	C22—C23	1.392 (6)
C4—H4A	0.9700	C22—C27	1.393 (5)
C4—H4B	0.9700	C23—C24	1.387 (6)
C5—O9	1.411 (5)	C23—H23	0.9300
C5—H5A	0.9700	C24—C25	1.379 (6)
C5—H5B	0.9700	C24—H24	0.9300
C6—O9	1.422 (6)	C25—C26	1.388 (5)
C6—C7	1.484 (6)	C25—H25	0.9300
C6—H6A	0.9700	C26—C27	1.374 (5)
C6—H6B	0.9700	C26—C28	1.508 (5)
C7—N3	1.448 (5)	C27—H27	0.9300
C7—H7A	0.9700	C28—O3	1.231 (5)
C7—H7B	0.9700	C28—O4	1.279 (4)
C8—C9	1.329 (7)	C29—O6	1.235 (5)
C8—N3	1.380 (6)	C29—O5	1.277 (5)
C8—H8	0.9300	C29—C30	1.494 (5)
C9—N4	1.370 (5)	C30—C31	1.377 (6)
C9—H9	0.9300	C30—C35	1.392 (5)
C10—N4	1.313 (5)	C31—C32	1.384 (6)
C10—N3	1.323 (5)	C31—H31	0.9300
C10—H10	0.9300	C32—C33	1.386 (6)
C11—N5	1.308 (5)	C32—H32	0.9300
C11—N6	1.318 (5)	C33—C34	1.381 (6)
C11—H11	0.9300	C33—H33	0.9300
C12—C13	1.352 (7)	C34—C35	1.378 (5)
C12—N5	1.371 (6)	C34—C36	1.511 (5)
C12—H12	0.9300	C35—H35	0.9300
C13—N6	1.337 (7)	C36—O7	1.231 (5)
C13—H13	0.9300	C36—O8	1.271 (5)
C14—C15	1.445 (7)	N4—Co2^iv	2.029 (3)
C14—N6	1.464 (6)	O4—Co1^v	2.011 (3)
C14—H14A	0.9700	O8—Co2^vi	1.989 (3)
C14—H14B	0.9700	O1W—H1A	1.00 (9)
C15—O10	1.381 (7)	O1W—H1B	0.83 (7)
C15—H15A	0.9700	O2W—H2A	0.84 (9)
C15—H15B	0.9700	O2W—H2B	0.86 (9)
C16—O10	1.406 (7)
O1—Co1—O4^i	94.52 (12)	C19—C18—H18	127.2
O1—Co1—N5	107.13 (14)	N7—C18—H18	127.2
O4^i—Co1—N5	122.46 (13)	C18—C19—N8	110.4 (4)
O1—Co1—N1	113.96 (13)	C18—C19—H19	124.8
O4^i—Co1—N1	105.31 (12)	N8—C19—H19	124.8
N5—Co1—N1	112.44 (14)	N8—C20—N7	111.2 (4)
O8^ii—Co2—O5	92.54 (12)	N8—C20—H20	124.4
O8^ii—Co2—N4^iii	117.28 (13)	N7—C20—H20	124.4
O5—Co2—N4^iii	114.84 (13)	O2—C21—O1	123.0 (4)
O8^ii—Co2—N8	106.00 (13)	O2—C21—C22	120.6 (4)
O5—Co2—N8	116.05 (13)	O1—C21—C22	116.4 (4)
N4^iii—Co2—N8	109.23 (14)	C23—C22—C27	118.9 (3)
N1—C1—N2	111.5 (4)	C23—C22—C21	121.3 (4)
N1—C1—H1	124.2	C27—C22—C21	119.8 (4)
N2—C1—H1	124.2	C24—C23—C22	119.7 (4)
C3—C2—N1	109.6 (4)	C24—C23—H23	120.1
C3—C2—H2	125.2	C22—C23—H23	120.1
N1—C2—H2	125.2	C25—C24—C23	120.8 (4)
C2—C3—N2	106.4 (4)	C25—C24—H24	119.6
C2—C3—H3	126.8	C23—C24—H24	119.6
N2—C3—H3	126.8	C24—C25—C26	119.8 (3)
N2—C4—C5	109.9 (4)	C24—C25—H25	120.1
N2—C4—H4A	109.7	C26—C25—H25	120.1
C5—C4—H4A	109.7	C27—C26—C25	119.7 (3)
N2—C4—H4B	109.7	C27—C26—C28	118.4 (3)
C5—C4—H4B	109.7	C25—C26—C28	122.0 (3)
H4A—C4—H4B	108.2	C26—C27—C22	121.2 (4)
O9—C5—C4	106.9 (4)	C26—C27—H27	119.4
O9—C5—H5A	110.3	C22—C27—H27	119.4
C4—C5—H5A	110.3	O3—C28—O4	121.5 (4)
O9—C5—H5B	110.3	O3—C28—C26	119.9 (4)
C4—C5—H5B	110.3	O4—C28—C26	118.5 (4)
H5A—C5—H5B	108.6	O6—C29—O5	121.4 (4)
O9—C6—C7	108.3 (4)	O6—C29—C30	120.3 (3)
O9—C6—H6A	110.0	O5—C29—C30	118.3 (4)
C7—C6—H6A	110.0	C31—C30—C35	118.8 (4)
O9—C6—H6B	110.0	C31—C30—C29	122.3 (3)
C7—C6—H6B	110.0	C35—C30—C29	118.9 (4)
H6A—C6—H6B	108.4	C30—C31—C32	120.8 (4)
N3—C7—C6	112.7 (4)	C30—C31—H31	119.6
N3—C7—H7A	109.0	C32—C31—H31	119.6
C6—C7—H7A	109.0	C31—C32—C33	119.7 (4)
N3—C7—H7B	109.0	C31—C32—H32	120.1
C6—C7—H7B	109.0	C33—C32—H32	120.1
H7A—C7—H7B	107.8	C34—C33—C32	120.1 (4)
C9—C8—N3	107.1 (4)	C34—C33—H33	119.9
C9—C8—H8	126.5	C32—C33—H33	119.9
N3—C8—H8	126.5	C35—C34—C33	119.5 (4)
C8—C9—N4	109.2 (4)	C35—C34—C36	118.8 (4)
C8—C9—H9	125.4	C33—C34—C36	121.7 (4)
N4—C9—H9	125.4	C34—C35—C30	121.0 (4)
N4—C10—N3	112.0 (4)	C34—C35—H35	119.5
N4—C10—H10	124.0	C30—C35—H35	119.5
N3—C10—H10	124.0	O7—C36—O8	123.0 (4)
N5—C11—N6	112.1 (4)	O7—C36—C34	119.5 (4)
N5—C11—H11	123.9	O8—C36—C34	117.5 (4)
N6—C11—H11	123.9	C1—N1—C2	105.1 (4)
C13—C12—N5	107.8 (5)	C1—N1—Co1	126.9 (3)
C13—C12—H12	126.1	C2—N1—Co1	127.3 (3)
N5—C12—H12	126.1	C1—N2—C3	107.3 (3)
N6—C13—C12	107.7 (5)	C1—N2—C4	126.4 (4)
N6—C13—H13	126.1	C3—N2—C4	126.1 (4)
C12—C13—H13	126.1	C10—N3—C8	106.1 (4)
C15—C14—N6	113.5 (4)	C10—N3—C7	126.7 (4)
C15—C14—H14A	108.9	C8—N3—C7	127.1 (4)
N6—C14—H14A	108.9	C10—N4—C9	105.6 (4)
C15—C14—H14B	108.9	C10—N4—Co2^iv	130.2 (3)
N6—C14—H14B	108.9	C9—N4—Co2^iv	124.0 (3)
H14A—C14—H14B	107.7	C11—N5—C12	105.4 (4)
O10—C15—C14	114.3 (5)	C11—N5—Co1	128.0 (3)
O10—C15—H15A	108.7	C12—N5—Co1	126.1 (3)
C14—C15—H15A	108.7	C11—N6—C13	106.9 (4)
O10—C15—H15B	108.7	C11—N6—C14	126.0 (4)
C14—C15—H15B	108.7	C13—N6—C14	127.1 (4)
H15A—C15—H15B	107.6	C20—N7—C18	107.9 (4)
O10—C16—C17	108.4 (5)	C20—N7—C17	124.9 (4)
O10—C16—H16A	110.0	C18—N7—C17	127.2 (4)
C17—C16—H16A	110.0	C20—N8—C19	104.9 (4)
O10—C16—H16B	110.0	C20—N8—Co2	126.2 (3)
C17—C16—H16B	110.0	C19—N8—Co2	128.9 (3)
H16A—C16—H16B	108.4	C21—O1—Co1	114.4 (3)
N7—C17—C16	113.6 (5)	C28—O4—Co1^v	103.1 (2)
N7—C17—H17A	108.9	C29—O5—Co2	103.1 (3)
C16—C17—H17A	108.9	C36—O8—Co2^vi	110.4 (3)
N7—C17—H17B	108.9	C5—O9—C6	112.5 (3)
C16—C17—H17B	108.9	C15—O10—C16	114.2 (5)
H17A—C17—H17B	107.7	H1A—O1W—H1B	88 (8)
C19—C18—N7	105.7 (4)	H2A—O2W—H2B	105 (9)
N1—C2—C3—N2	0.0 (5)	N4—C10—N3—C8	1.0 (5)
N2—C4—C5—O9	−177.2 (4)	N4—C10—N3—C7	178.3 (4)
O9—C6—C7—N3	72.2 (5)	C9—C8—N3—C10	−1.1 (6)
N3—C8—C9—N4	0.9 (6)	C9—C8—N3—C7	−178.4 (4)
N5—C12—C13—N6	0.2 (8)	C6—C7—N3—C10	−101.1 (5)
N6—C14—C15—O10	63.9 (8)	C6—C7—N3—C8	75.6 (6)
O10—C16—C17—N7	−69.4 (6)	N3—C10—N4—C9	−0.4 (5)
N7—C18—C19—N8	0.5 (6)	N3—C10—N4—Co2^iv	−175.2 (3)
O2—C21—C22—C23	−164.7 (4)	C8—C9—N4—C10	−0.3 (6)
O1—C21—C22—C23	15.0 (6)	C8—C9—N4—Co2^iv	174.8 (3)
O2—C21—C22—C27	17.4 (6)	N6—C11—N5—C12	−0.8 (5)
O1—C21—C22—C27	−162.9 (4)	N6—C11—N5—Co1	−173.2 (3)
C27—C22—C23—C24	−1.8 (6)	C13—C12—N5—C11	0.3 (7)
C21—C22—C23—C24	−179.6 (4)	C13—C12—N5—Co1	172.9 (4)
C22—C23—C24—C25	0.8 (6)	O1—Co1—N5—C11	−111.2 (4)
C23—C24—C25—C26	0.8 (6)	O4^i—Co1—N5—C11	−4.1 (4)
C24—C25—C26—C27	−1.4 (6)	N1—Co1—N5—C11	122.9 (4)
C24—C25—C26—C28	176.9 (4)	O1—Co1—N5—C12	77.9 (5)
C25—C26—C27—C22	0.4 (6)	O4^i—Co1—N5—C12	−175.0 (4)
C28—C26—C27—C22	−177.9 (3)	N1—Co1—N5—C12	−48.0 (5)
C23—C22—C27—C26	1.2 (6)	N5—C11—N6—C13	0.9 (6)
C21—C22—C27—C26	179.1 (3)	N5—C11—N6—C14	−177.7 (4)
C27—C26—C28—O3	17.1 (6)	C12—C13—N6—C11	−0.7 (7)
C25—C26—C28—O3	−161.1 (4)	C12—C13—N6—C14	178.0 (5)
C27—C26—C28—O4	−160.2 (3)	C15—C14—N6—C11	−99.5 (7)
C25—C26—C28—O4	21.5 (5)	C15—C14—N6—C13	82.1 (8)
O6—C29—C30—C31	−168.5 (4)	N8—C20—N7—C18	0.1 (6)
O5—C29—C30—C31	11.9 (6)	N8—C20—N7—C17	177.1 (5)
O6—C29—C30—C35	11.1 (6)	C19—C18—N7—C20	−0.4 (6)
O5—C29—C30—C35	−168.5 (4)	C19—C18—N7—C17	−177.3 (5)
C35—C30—C31—C32	−2.3 (7)	C16—C17—N7—C20	−98.0 (6)
C29—C30—C31—C32	177.4 (4)	C16—C17—N7—C18	78.5 (7)
C30—C31—C32—C33	1.6 (8)	N7—C20—N8—C19	0.2 (5)
C31—C32—C33—C34	0.9 (8)	N7—C20—N8—Co2	−177.8 (3)
C32—C33—C34—C35	−2.6 (7)	C18—C19—N8—C20	−0.5 (6)
C32—C33—C34—C36	177.5 (4)	C18—C19—N8—Co2	177.5 (4)
C33—C34—C35—C30	1.9 (6)	O8^ii—Co2—N8—C20	51.5 (4)
C36—C34—C35—C30	−178.2 (3)	O5—Co2—N8—C20	152.5 (4)
C31—C30—C35—C34	0.5 (6)	N4^iii—Co2—N8—C20	−75.8 (4)
C29—C30—C35—C34	−179.1 (3)	O8^ii—Co2—N8—C19	−126.1 (4)
C35—C34—C36—O7	7.7 (6)	O5—Co2—N8—C19	−25.1 (4)
C33—C34—C36—O7	−172.4 (4)	N4^iii—Co2—N8—C19	106.6 (4)
C35—C34—C36—O8	−171.3 (4)	O2—C21—O1—Co1	−13.1 (6)
C33—C34—C36—O8	8.6 (6)	C22—C21—O1—Co1	167.2 (3)
N2—C1—N1—C2	0.3 (5)	O4^i—Co1—O1—C21	174.0 (3)
N2—C1—N1—Co1	171.2 (3)	N5—Co1—O1—C21	−60.0 (3)
C3—C2—N1—C1	−0.1 (5)	N1—Co1—O1—C21	65.1 (3)
C3—C2—N1—Co1	−171.0 (3)	O3—C28—O4—Co1^v	−12.1 (4)
O1—Co1—N1—C1	−15.6 (4)	C26—C28—O4—Co1^v	165.3 (3)
O4^i—Co1—N1—C1	−117.8 (3)	O6—C29—O5—Co2	−6.1 (5)
N5—Co1—N1—C1	106.5 (4)	C30—C29—O5—Co2	173.5 (3)
O1—Co1—N1—C2	153.3 (3)	O8^ii—Co2—O5—C29	178.7 (3)
O4^i—Co1—N1—C2	51.1 (4)	N4^iii—Co2—O5—C29	−59.5 (3)
N5—Co1—N1—C2	−84.5 (4)	N8—Co2—O5—C29	69.6 (3)
N1—C1—N2—C3	−0.3 (5)	O7—C36—O8—Co2^vi	−11.3 (5)
N1—C1—N2—C4	−175.4 (4)	C34—C36—O8—Co2^vi	167.7 (3)
C2—C3—N2—C1	0.2 (5)	C4—C5—O9—C6	−169.4 (4)
C2—C3—N2—C4	175.3 (4)	C7—C6—O9—C5	−175.2 (4)
C5—C4—N2—C1	101.4 (5)	C14—C15—O10—C16	167.2 (5)
C5—C4—N2—C3	−72.8 (6)	C17—C16—O10—C15	−178.9 (6)

Symmetry codes: (i) x−1/2, y+1/2, z; (ii) x−1/2, y−1/2, z; (iii) x−1, y, z; (iv) x+1, y, z; (v) x+1/2, y−1/2, z; (vi) x+1/2, y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2	1.00 (9)	1.87 (9)	2.830 (6)	158 (8)
O1W—H1B···O6^v	0.83 (7)	1.99 (4)	2.773 (5)	157 (9)
O2W—H2A···O7^vii	0.84 (9)	2.12 (9)	2.929 (6)	160 (9)

Symmetry codes: (v) x+1/2, y−1/2, z; (vii) x, y−1, z.