Bis[tris­(2,2'-bipyridyl-[kappa]²N,N')cobalt(II)] cyclo-tetra­vanadate undeca­hydrate

The title compound, [Co(C₁₀H₈N₂)₃]₂[V₄O₁₂]·11H₂O, is com­posed of two symmetry-related cations containing octa­hedrally coordinated Co^II ions, a centrosymmetric [V₄O₁₂]^4- anion with an eight-membered ring structure made up of four VO₄ tetra­hedra, and 11 solvent water mol­ecules. The Co^II cations and vanadate anions are isolated and build cation and anion layers, respectively. In addition, the title compound exhibits a three-dimensional network through intra- and inter­molecular hydrogen-bond inter­actions between water mol­ecules and O atoms of the anions, and the crystal structure is stabilized mainly by hydrogen bonds.

S1. Comment

The design and synthesis of novel vanadium oxides have been the subject of growing interest, due not only to their structural diversity but also to their wide-ranging potential activities, such as efficient catalysis (Yazigi et al., 2010), magnetic properties (Saldias et al., 2012; Zhang et al., 2003, 2007) and electrochemical properties (Zhang et al., 2012). In the past two decades, a large number of compounds of the form [M'L_x]ⁿ⁺ (M' is a transition metal and L is a ligand) connected directly to [V_yO_z]^n- anion clusters (M'—O—V) have been reported, such as [Cu₂(2,2'-bpy)₂V₈O₂₁]_n (bpy is bipyridine; Yu & Kong, 2010), [{Mn(phen)₂}₂V₄O₁₂].0.5H₂O (phen is 1,10-phenanthroline; Lu, Wang, Yuan, Li et al., 2002), [{Co(phen)₂}₂V₄O₁₂].H₂O (Kucsera et al., 2002), [{Zn(2,2'-bpy)}₂V₈O₂₁] (Xiao, Hou et al., 2004), [Ti(2,2'-bpy)V₂O₇] (Xiao, Wang, Hou et al., 2004), [Co(2,2'-bpy)₂V₃O_8.5] (Xiao, Wang, An et al., 2004), [Co(2,2'-bpy)(VO₃)₂(H₂O)] (Lin, Pei & Liu, 2003), [Mn(2,2'-bpy)₂V₂O₆] (Devi & Zubieta, 2002) and [{Cu(phen)₂}₄V₁₀O₂₉].6H₂O (Zhang et al., 2000). Some [M'L_x]ⁿ⁺ compounds isolated from [V_yO_z]^n- anion clusters have also been reported, examples being [Co(phen)₃][V₁₀O₂₆].H₂O (Lu et al., 2004), [Fe(2,2'-bpy)₃]₂[V₄O₁₂].10H₂O, (II) (Huang et al., 2004), [Ni(2,2'-bpy)₃]₂[V₄O₁₂].11H₂O, (III) (Yang et al., 1998), [Zn(2,2'-bpy)₃]₂[V₄O₁₂].11H₂O, (IV) (Zhang et al., 1997) and Co(dien)₂(VO₃)₃.H₂O (dien is diethylenetriamine; Lin, Li et al., 2003). The Fe-, Ni- and Zn-containing compounds are apparently isostructural (Yang et al., 1998). The [V₄O₁₂]^4- anions and [M'(2,2'-bpy)₃]²⁺ (M' = Fe, Ni and Zn) cations form layers separated by water molecules. In order to enrich the range of isostructural compounds, we have recently synthesized [Co(bpy)₃]₂[V₄O₁₂].11H₂O, (I), with Co as the transition metal, and present its structure here.

The asymmetric unit of (I) (Fig. 1) consists of one [Co(bpy)₃]²⁺ cation, half a [V₄O₁₂]^4- anion (which is located around a centre of inversion) and five and a half water molecules (the half molecule being located on a twofold axis). In the [Co(bpy)₃]²⁺ cation, the central Co^II atom is coordinated by six N atoms from three 2,2'-bipyridine (2,2'-bpy) groups and each Co^II centre exhibits a slightly distorted octahedral coordination geometry. The Co—N bond lengths range from 2.113 (3) to 2.153 (3) Å and the N—Co—N angles are in the range 76.81 (11)–169.65 (11)°. In the [V₄O₁₂]^4- anion, the V and bridging O atoms form an eight-membered ring, with V—O_b (b denotes bridging) bond lengths in the range 1.788 (2)–1.798 (2) Å; the V—O_t (t denotes terminal) bond lengths are in the range 1.618 (2)–1.636 (3) Å. On the basis of valence-sum calculations (Brown & Altermatt, 1985), atoms V1 and V2 are pentavalent; this value is consistent with the overall charge balance of the compound. Each [V₄O₁₂]^4- anion consists of four distorted VO₄ tetrahedra.

In the structure of (I), the [V₄O₁₂]^4- anion layers are separated by an interlamellar region occupied by the [Co(bpy)₃]²⁺ cations (Huang et al., 2004) (Fig. 2). The [Co(bpy)₃]²⁺ cations play a significant role in filling the layers assembled by the [V₄O₁₂]^4- anions and water molecules via hydrogen-bonding interactions and in fulfilling the charge balance of the compound (Fig. 3). The cations are beautifully arranged to form rings, where one bipy ligand from each of six cations is directed towards water molecule O1W located at (1/2, 1/2, 0) (Fig. 4).

The asymmetric unit contains O1W—H1W···O6, O2W—H2D···O5, O2W—H2C···O3, O3W—H3C···O5ⁱ, O3W—H3D···O6W, O4W—H4D···O5W, O4W—H4E···O6W, O5W—H5E···O4W, O6W—H6C···O2 and O6W—H6E···O4W (Table 1 and Fig. 5) hydrogen bonds. Two adjacent [V₄O₁₂]^4- anions are linked through O1W—H1W···O6, O4W—H4C···O3ⁱⁱⁱ, O4W—H4E···O6W, O6W—H6E···O4W, O6W—H6C···O2, O6W—H6D···O3W, O3W—H3C···O5ⁱ, O3W—H3D···O6W and O3W—H3E···O3Wⁱⁱ (Table 1 and Fig. 6) hydrogen bonds. A two-dimensional layer of [V₄O₁₂]^4- anion clusters is formed through O···H—OW and OW···OW interactions (Fig. 6). These strong hydrogen bonds are of great importance in the constitution of the three-dimensional network and in the stabilization of the structure.

In the IR spectrum of (I), the characteristic bands at 1017, 917, 790, 664 and 526 cm^-1 are assigned to terminal (V═O) and bridging (V—O—V) stretching. The peaks in the 1632–1166 cm^-1 region are due to the 2,2'-bipy groups (Lu, Wang, Yuan, Luan et al., 2002). In addition, the weak bands at 3855 and 3738 cm^-1 correspond to O—H stretching of water molecules. The presence of a broad band at 3435 cm^-1 was assigned to C—H stretching (Lu, Wang, Yuan, Li et al., 2002) (see Fig. S1 in the Supplementary materials).

The UV spectrum of (I) in solution in distilled water exhibits a strong band around 200 nm ascribed to the ligand-to-metal charge-transfer (LMCT) transition of terminal O atoms to vanadium (Li et al., 2002). A weak band around 300 nm corresponds to a ligand-centred π–π* transition (Fay et al., 2003) (see Fig. S2 in the Supplementary materials).

In conclusion, we have successfully synthesized a three-dimensional Co^II compound, and postulate that the use of different transition metal ions in compounds of this type may have a significant effect on the formation of the resulting structure. [Rephrasing OK?]

Related literature

For related literature, see: Brown & Altermatt (1985); Devi & Zubieta (2002); Fay et al. (2003); Huang et al. (2004); Kucsera et al. (2002); Li et al. (2002); Lin, Li, Pei & Liu (2003); Lin, Pei & Liu (2003); Lu et al. (2004); Lu, Wang, Yuan, Li, Xua, Hu, Hu & Jia (2002); Lu, Wang, Yuan, Luan, Li, Zhang, Hu, Yao, Qin & Chen (2002); Saldias et al. (2012); Xiao, Hou, Wang, Li, Lü, Xu & Hu (2004); Xiao, Wang, An, Xu & Hu (2004); Xiao, Wang, Hou, Wang, Li, An, Xu & Hu (2004); Yang et al. (1998); Yazigi et al. (2010); Yu & Kong (2010); Zhang et al. (1997, 2000, 2003, 2007, 2012).

S2. Experimental

A mixture of Co(NO₃)₂.6H₂O (0.110 g, 0.378 mmol), NH₄VO₃ (0.082 g, 0.701 mmol), 2,2'-bipy (0.045 g, 0.288 mmol) and H₂O (10 ml) was stirred for 30 min, after which time the pH was adjusted to 2.0 using 3 M HCl. The mixture was transferred to a Teflon-lined autoclave (25 ml) with 60% filling and kept at 433 K for 5 d. The pink crystals of (I) which formed were filtered off, washed with distilled water and dried in air at room temperature. Elemental analysis, calculated: H 4.17, C 43.56, N 10.26%; experimental: H 4.25, C 43.67, N 10.18%.

S3. Refinement

All H atoms were located geometrically and then refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). For the water molecules, O1W—H1W = 0.82 Å and O2W—H2W = 0.82 Å. The H atoms of O3W, O4W, O5W and O6W are disordered over three sites in the refinement [with occupancies of..?].

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level. H atoms have been omitted for clarity. Fig. 2. A packing diagram for (I), viewed normal to the ac plane. Dashed lines indicate hydrogen bonds. H atoms have been omitted for clarity. Fig. 3. The [Co(bpy)3]^2+ cations in the layers constructed from [V4O12]^4- anions and water molecules. Dashed lines indicate hydrogen bonds. H atoms of the 2,2'-bipy groups have been omitted for clarity. Fig. 4. A view of the cations forming a six-membered ring in the ab plane. H atoms have been omitted for clarity. Fig. 5. The intramolecular hydrogen-bonding interactions (dashed lines) of (I). The cations have been omitted. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.] Fig. 6. The two-dimensional layers of [V4O12]^4- anions and water formed by hydrogen-bonding interactions (dashed lines) in (I). [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1/2, -y + 1/2, -z + 1; (iii) -x + 1/2, -y + 3/2, -z + 1; (iv) x - 1/2, y - 1/2, z; (v) -x, -y + 1, -z + 1.]

Bis[tris(2,2'-bipyridyl-κ²N,N')cobalt(II)] cyclo-tetravanadate undecahydrate

Crystal data

[Co(C10H8N2)3]2[V4O12]·11H2O	F(000) = 3376
Mr = 1648.90	Dx = 1.555 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5706 reflections
a = 21.965 (3) Å	θ = 2.3–26.0°
b = 14.003 (2) Å	µ = 1.05 mm^−1
c = 23.836 (4) Å	T = 298 K
β = 106.080 (3)°	Block, pink
V = 7044.5 (19) Å^3	0.26 × 0.24 × 0.22 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	6970 independent reflections
Radiation source: fine-focus sealed tube	4505 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ϕ and ω scans	θmax = 26.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→27
Tmin = 0.768, Tmax = 0.793	k = −14→17
18756 measured reflections	l = −29→29

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) = 0.104	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.045P)^2 + 0.3P] where P = (Fo^2 + 2Fc^2)/3
6913 reflections	(Δ/σ)max = 0.001
456 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.26 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	Occ. (<1)
Co1	0.16862 (2)	0.53585 (3)	0.266412 (19)	0.03081 (13)
N1	0.22446 (13)	0.5894 (2)	0.21193 (12)	0.0365 (7)
N2	0.26007 (13)	0.48287 (19)	0.30790 (12)	0.0338 (7)
N3	0.14253 (13)	0.4068 (2)	0.21766 (12)	0.0372 (7)
N4	0.12247 (12)	0.45585 (19)	0.31836 (12)	0.0326 (7)
N5	0.17747 (13)	0.6650 (2)	0.31621 (12)	0.0357 (7)
N6	0.08783 (12)	0.6151 (2)	0.22106 (11)	0.0331 (7)
C1	0.2408 (2)	0.6591 (3)	0.12552 (17)	0.0599 (12)
H1A	0.2248	0.6943	0.0915	0.072*
C2	0.20338 (19)	0.6386 (3)	0.16195 (16)	0.0510 (10)
H2A	0.1616	0.6599	0.1514	0.061*
C3	0.3019 (2)	0.6264 (3)	0.14068 (18)	0.0588 (12)
H3A	0.3278	0.6379	0.1164	0.071*
C4	0.32481 (18)	0.5768 (3)	0.19166 (17)	0.0485 (10)
H4A	0.3665	0.5553	0.2026	0.058*
C5	0.28516 (16)	0.5588 (2)	0.22697 (15)	0.0361 (8)
C6	0.30648 (16)	0.5060 (2)	0.28306 (15)	0.0342 (8)
C7	0.36857 (17)	0.4822 (3)	0.30831 (17)	0.0452 (10)
H7A	0.3997	0.4986	0.2903	0.054*
C8	0.38442 (17)	0.4336 (3)	0.36070 (17)	0.0470 (10)
H8A	0.4264	0.4178	0.3786	0.056*
C9	0.33855 (18)	0.4090 (3)	0.38594 (16)	0.0479 (10)
H9A	0.3484	0.3754	0.4209	0.058*
C10	0.27645 (18)	0.4351 (3)	0.35842 (15)	0.0440 (9)
H10A	0.2449	0.4187	0.3759	0.053*
C11	0.15272 (19)	0.3862 (3)	0.16625 (16)	0.0492 (10)
H11A	0.1729	0.4317	0.1493	0.059*
C12	0.13514 (19)	0.3019 (3)	0.13706 (17)	0.0531 (11)
H12A	0.1435	0.2903	0.1015	0.064*
C13	0.10487 (19)	0.2349 (3)	0.16186 (18)	0.0559 (11)
H13A	0.0921	0.1770	0.1432	0.067*
C14	0.09369 (18)	0.2546 (3)	0.21466 (17)	0.0518 (10)
H14A	0.0736	0.2097	0.2321	0.062*
C15	0.11245 (15)	0.3412 (2)	0.24174 (15)	0.0351 (8)
C16	0.10165 (15)	0.3685 (3)	0.29823 (15)	0.0353 (8)
C17	0.07194 (19)	0.3086 (3)	0.32906 (18)	0.0555 (11)
H17A	0.0581	0.2484	0.3146	0.067*
C18	0.0632 (2)	0.3390 (3)	0.38071 (18)	0.0628 (12)
H18A	0.0428	0.3000	0.4014	0.075*
C19	0.0848 (2)	0.4276 (3)	0.40183 (17)	0.0560 (11)
H19A	0.0800	0.4491	0.4373	0.067*
C20	0.11369 (17)	0.4836 (3)	0.36976 (16)	0.0447 (10)
H20A	0.1280	0.5438	0.3841	0.054*
C21	0.22066 (17)	0.6825 (3)	0.36698 (16)	0.0454 (10)
H21A	0.2521	0.6373	0.3815	0.054*
C22	0.22045 (19)	0.7648 (3)	0.39866 (17)	0.0534 (11)
H22A	0.2502	0.7739	0.4345	0.064*
C23	0.1754 (2)	0.8334 (3)	0.37625 (18)	0.0562 (11)
H23A	0.1746	0.8898	0.3966	0.067*
C24	0.13160 (18)	0.8173 (3)	0.32334 (16)	0.0470 (10)
H24A	0.1011	0.8631	0.3072	0.056*
C25	0.13355 (15)	0.7320 (2)	0.29438 (15)	0.0343 (8)
C26	0.08631 (15)	0.7075 (2)	0.23845 (14)	0.0315 (8)
C27	0.04415 (16)	0.7720 (3)	0.20550 (15)	0.0409 (9)
H27A	0.0433	0.8345	0.2185	0.049*
C28	0.00304 (17)	0.7439 (3)	0.15296 (16)	0.0444 (10)
H28A	−0.0247	0.7874	0.1296	0.053*
C29	0.00407 (16)	0.6506 (3)	0.13605 (16)	0.0441 (10)
H29A	−0.0235	0.6296	0.1012	0.053*
C30	0.04627 (16)	0.5883 (3)	0.17121 (15)	0.0414 (9)
H30A	0.0458	0.5247	0.1598	0.050*
V1	0.42366 (3)	0.62888 (4)	0.49574 (2)	0.03422 (16)
V2	0.53755 (3)	0.56779 (4)	0.42423 (2)	0.03419 (16)
O1	0.44484 (12)	0.55579 (17)	0.56024 (10)	0.0457 (6)
O2	0.34856 (11)	0.6210 (2)	0.46378 (11)	0.0605 (8)
O3	0.43964 (13)	0.73971 (18)	0.51606 (11)	0.0556 (7)
O4	0.46786 (11)	0.59514 (18)	0.44592 (10)	0.0477 (7)
O5	0.59616 (12)	0.63575 (19)	0.45973 (12)	0.0589 (8)
O6	0.52449 (12)	0.58691 (18)	0.35450 (10)	0.0518 (7)
O1W	0.5000	0.4876 (3)	0.2500	0.0611 (11)
H1W	0.5056	0.5208	0.2793	0.092*
O2W	0.57072 (14)	0.7844 (2)	0.53342 (13)	0.0752 (9)
H2C	0.5330	0.7780	0.5311	0.113*
H2D	0.5844	0.7511	0.5113	0.113*
O3W	0.27504 (14)	0.3360 (2)	0.49023 (13)	0.0825 (10)
H3C	0.3121	0.3293	0.5093	0.124*
H3D	0.2587	0.3872	0.4943	0.124*	0.50
H3E	0.2496	0.2988	0.4979	0.124*	0.50
O4W	0.13959 (15)	0.6044 (2)	0.50320 (16)	0.0964 (12)
H4C	0.1244	0.6580	0.4960	0.145*
H4D	0.1372	0.5806	0.5340	0.145*	0.50
H4E	0.1667	0.5897	0.4871	0.145*	0.50
O5W	0.05950 (18)	0.4838 (2)	0.54174 (15)	0.0946 (12)
H5C	0.0680	0.4281	0.5363	0.142*
H5D	0.0335	0.5098	0.5146	0.142*	0.50
H5E	0.0833	0.5242	0.5345	0.142*	0.50
O6W	0.24914 (16)	0.5289 (3)	0.49331 (18)	0.1103 (13)
H6C	0.2771	0.5561	0.4826	0.165*
H6D	0.2569	0.4718	0.4926	0.165*	0.50
H6E	0.2129	0.5415	0.4704	0.165*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0313 (3)	0.0300 (3)	0.0309 (3)	0.0003 (2)	0.0083 (2)	0.0010 (2)
N1	0.0424 (18)	0.0350 (18)	0.0343 (17)	0.0032 (14)	0.0144 (14)	0.0061 (14)
N2	0.0318 (15)	0.0326 (18)	0.0354 (16)	0.0040 (13)	0.0065 (13)	0.0034 (13)
N3	0.0418 (17)	0.0326 (18)	0.0364 (17)	−0.0007 (14)	0.0095 (14)	−0.0047 (14)
N4	0.0334 (15)	0.0325 (17)	0.0327 (16)	−0.0006 (13)	0.0106 (13)	−0.0014 (13)
N5	0.0325 (16)	0.0398 (19)	0.0326 (17)	−0.0023 (14)	0.0055 (13)	−0.0007 (14)
N6	0.0318 (15)	0.0341 (18)	0.0310 (16)	−0.0012 (13)	0.0048 (13)	−0.0003 (13)
C1	0.079 (3)	0.064 (3)	0.043 (2)	0.008 (3)	0.027 (2)	0.019 (2)
C2	0.054 (2)	0.055 (3)	0.046 (2)	0.008 (2)	0.018 (2)	0.014 (2)
C3	0.069 (3)	0.068 (3)	0.051 (3)	−0.004 (3)	0.037 (2)	0.010 (2)
C4	0.043 (2)	0.056 (3)	0.054 (3)	0.001 (2)	0.025 (2)	0.002 (2)
C5	0.039 (2)	0.031 (2)	0.040 (2)	−0.0010 (17)	0.0126 (17)	−0.0034 (16)
C6	0.0330 (19)	0.032 (2)	0.038 (2)	−0.0006 (16)	0.0101 (16)	−0.0048 (16)
C7	0.037 (2)	0.047 (3)	0.053 (2)	0.0008 (19)	0.0148 (19)	−0.001 (2)
C8	0.033 (2)	0.048 (3)	0.054 (3)	0.0067 (19)	0.0013 (19)	−0.008 (2)
C9	0.050 (2)	0.048 (3)	0.039 (2)	0.011 (2)	0.0016 (19)	0.0058 (19)
C10	0.045 (2)	0.049 (3)	0.038 (2)	0.0058 (19)	0.0121 (18)	0.0084 (19)
C11	0.064 (3)	0.049 (3)	0.037 (2)	−0.001 (2)	0.016 (2)	−0.0071 (19)
C12	0.065 (3)	0.053 (3)	0.040 (2)	0.002 (2)	0.013 (2)	−0.013 (2)
C13	0.064 (3)	0.042 (3)	0.054 (3)	−0.002 (2)	0.002 (2)	−0.018 (2)
C14	0.060 (3)	0.039 (2)	0.053 (3)	−0.007 (2)	0.009 (2)	−0.005 (2)
C15	0.0332 (19)	0.029 (2)	0.039 (2)	0.0004 (16)	0.0046 (16)	−0.0011 (17)
C16	0.0324 (19)	0.034 (2)	0.038 (2)	0.0000 (17)	0.0070 (16)	0.0033 (17)
C17	0.068 (3)	0.040 (3)	0.060 (3)	−0.011 (2)	0.021 (2)	0.004 (2)
C18	0.083 (3)	0.059 (3)	0.054 (3)	−0.015 (3)	0.032 (2)	0.011 (2)
C19	0.075 (3)	0.061 (3)	0.042 (2)	−0.004 (2)	0.032 (2)	0.003 (2)
C20	0.049 (2)	0.042 (2)	0.045 (2)	−0.0042 (19)	0.0161 (19)	−0.0058 (19)
C21	0.039 (2)	0.044 (2)	0.047 (2)	0.0011 (19)	0.0020 (18)	−0.0016 (19)
C22	0.057 (3)	0.054 (3)	0.041 (2)	−0.013 (2)	0.001 (2)	−0.013 (2)
C23	0.065 (3)	0.046 (3)	0.054 (3)	−0.010 (2)	0.011 (2)	−0.017 (2)
C24	0.052 (2)	0.035 (2)	0.052 (2)	0.0034 (19)	0.010 (2)	−0.0039 (19)
C25	0.0328 (19)	0.035 (2)	0.037 (2)	−0.0042 (17)	0.0124 (16)	−0.0017 (17)
C26	0.0325 (19)	0.031 (2)	0.0322 (19)	−0.0002 (16)	0.0110 (15)	0.0031 (16)
C27	0.048 (2)	0.033 (2)	0.043 (2)	0.0065 (18)	0.0153 (18)	0.0046 (18)
C28	0.041 (2)	0.054 (3)	0.038 (2)	0.012 (2)	0.0101 (18)	0.010 (2)
C29	0.036 (2)	0.058 (3)	0.035 (2)	0.002 (2)	0.0045 (17)	0.003 (2)
C30	0.039 (2)	0.043 (2)	0.038 (2)	−0.0047 (18)	0.0038 (17)	−0.0045 (18)
V1	0.0341 (3)	0.0337 (4)	0.0324 (3)	0.0060 (3)	0.0050 (3)	0.0019 (3)
V2	0.0385 (3)	0.0331 (4)	0.0306 (3)	0.0010 (3)	0.0092 (3)	0.0023 (3)
O1	0.0546 (16)	0.0407 (16)	0.0426 (15)	0.0102 (13)	0.0150 (12)	0.0073 (12)
O2	0.0404 (15)	0.083 (2)	0.0527 (17)	0.0051 (15)	0.0042 (13)	0.0029 (16)
O3	0.0788 (19)	0.0309 (15)	0.0533 (17)	0.0035 (14)	0.0118 (14)	−0.0043 (13)
O4	0.0497 (16)	0.0537 (17)	0.0423 (15)	0.0108 (14)	0.0170 (12)	0.0050 (13)
O5	0.0532 (17)	0.0527 (18)	0.0661 (19)	−0.0099 (14)	0.0089 (14)	−0.0104 (15)
O6	0.0714 (19)	0.0493 (17)	0.0365 (15)	0.0032 (15)	0.0178 (13)	0.0072 (13)
O1W	0.091 (3)	0.047 (3)	0.053 (2)	0.000	0.032 (2)	0.000
O2W	0.079 (2)	0.063 (2)	0.091 (2)	−0.0037 (17)	0.0357 (18)	−0.0173 (18)
O3W	0.063 (2)	0.107 (3)	0.082 (2)	−0.0272 (19)	0.0261 (17)	−0.020 (2)
O4W	0.092 (3)	0.056 (2)	0.150 (3)	0.0163 (19)	0.048 (2)	−0.005 (2)
O5W	0.145 (3)	0.062 (2)	0.091 (3)	−0.007 (2)	0.057 (2)	−0.0002 (19)
O6W	0.070 (2)	0.119 (3)	0.154 (4)	−0.002 (2)	0.052 (2)	0.014 (3)

Geometric parameters (Å, º)

Co1—N2	2.113 (3)	C18—C19	1.373 (5)
Co1—N6	2.118 (3)	C18—H18A	0.9300
Co1—N4	2.124 (3)	C19—C20	1.367 (5)
Co1—N3	2.139 (3)	C19—H19A	0.9300
Co1—N5	2.143 (3)	C20—H20A	0.9300
Co1—N1	2.153 (3)	C21—C22	1.379 (5)
N1—C2	1.343 (4)	C21—H21A	0.9300
N1—C5	1.351 (4)	C22—C23	1.376 (5)
N2—C10	1.337 (4)	C22—H22A	0.9300
N2—C6	1.352 (4)	C23—C24	1.377 (5)
N3—C11	1.337 (4)	C23—H23A	0.9300
N3—C15	1.349 (4)	C24—C25	1.387 (5)
N4—C16	1.346 (4)	C24—H24A	0.9300
N4—C20	1.349 (4)	C25—C26	1.485 (5)
N5—C21	1.337 (4)	C26—C27	1.374 (4)
N5—C25	1.342 (4)	C27—C28	1.383 (5)
N6—C30	1.336 (4)	C27—H27A	0.9300
N6—C26	1.361 (4)	C28—C29	1.368 (5)
C1—C3	1.370 (6)	C28—H28A	0.9300
C1—C2	1.381 (5)	C29—C30	1.376 (5)
C1—H1A	0.9300	C29—H29A	0.9300
C2—H2A	0.9300	C30—H30A	0.9300
C3—C4	1.369 (5)	V1—O2	1.618 (2)
C3—H3A	0.9300	V1—O3	1.635 (3)
C4—C5	1.392 (5)	V1—O4	1.793 (2)
C4—H4A	0.9300	V1—O1	1.798 (2)
C5—C6	1.486 (5)	V2—O6	1.629 (2)
C6—C7	1.370 (5)	V2—O5	1.636 (3)
C7—C8	1.380 (5)	V2—O4	1.788 (2)
C7—H7A	0.9300	V2—O1^i	1.789 (2)
C8—C9	1.353 (5)	O1—V2^i	1.789 (2)
C8—H8A	0.9300	O1W—H1W	0.8200
C9—C10	1.389 (5)	O2W—H2C	0.8201
C9—H9A	0.9300	O2W—H2D	0.8200
C10—H10A	0.9300	O3W—H3C	0.8199
C11—C12	1.370 (5)	O3W—H3D	0.8199
C11—H11A	0.9300	O3W—H3E	0.8202
C12—C13	1.374 (5)	O4W—H4C	0.8198
C12—H12A	0.9300	O4W—H4D	0.8202
C13—C14	1.375 (5)	O4W—H4E	0.8200
C13—H13A	0.9300	O5W—H5C	0.8199
C14—C15	1.382 (5)	O5W—H5D	0.8201
C14—H14A	0.9300	O5W—H5E	0.8201
C15—C16	1.481 (5)	O6W—H6C	0.8200
C16—C17	1.391 (5)	O6W—H6D	0.8199
C17—C18	1.365 (5)	O6W—H6E	0.8500
C17—H17A	0.9300
N2—Co1—N6	167.54 (11)	N3—C15—C14	121.1 (3)
N2—Co1—N4	95.01 (11)	N3—C15—C16	115.6 (3)
N6—Co1—N4	96.10 (10)	C14—C15—C16	123.3 (3)
N2—Co1—N3	91.99 (11)	N4—C16—C17	121.5 (3)
N6—Co1—N3	96.02 (11)	N4—C16—C15	115.8 (3)
N4—Co1—N3	76.81 (11)	C17—C16—C15	122.8 (3)
N2—Co1—N5	96.23 (10)	C18—C17—C16	119.5 (4)
N6—Co1—N5	77.00 (11)	C18—C17—H17A	120.3
N4—Co1—N5	96.15 (10)	C16—C17—H17A	120.3
N3—Co1—N5	169.65 (11)	C17—C18—C19	119.4 (4)
N2—Co1—N1	77.17 (11)	C17—C18—H18A	120.3
N6—Co1—N1	92.66 (11)	C19—C18—H18A	120.3
N4—Co1—N1	168.22 (11)	C20—C19—C18	118.7 (4)
N3—Co1—N1	94.47 (11)	C20—C19—H19A	120.7
N5—Co1—N1	93.48 (11)	C18—C19—H19A	120.7
C2—N1—C5	118.1 (3)	N4—C20—C19	123.2 (4)
C2—N1—Co1	126.9 (2)	N4—C20—H20A	118.4
C5—N1—Co1	114.5 (2)	C19—C20—H20A	118.4
C10—N2—C6	117.8 (3)	N5—C21—C22	122.7 (4)
C10—N2—Co1	125.5 (2)	N5—C21—H21A	118.7
C6—N2—Co1	116.5 (2)	C22—C21—H21A	118.7
C11—N3—C15	118.0 (3)	C23—C22—C21	118.8 (4)
C11—N3—Co1	126.4 (3)	C23—C22—H22A	120.6
C15—N3—Co1	115.7 (2)	C21—C22—H22A	120.6
C16—N4—C20	117.7 (3)	C22—C23—C24	119.1 (4)
C16—N4—Co1	116.2 (2)	C22—C23—H23A	120.4
C20—N4—Co1	126.1 (2)	C24—C23—H23A	120.4
C21—N5—C25	118.5 (3)	C23—C24—C25	119.1 (4)
C21—N5—Co1	126.1 (3)	C23—C24—H24A	120.4
C25—N5—Co1	115.4 (2)	C25—C24—H24A	120.4
C30—N6—C26	118.0 (3)	N5—C25—C24	121.8 (3)
C30—N6—Co1	125.2 (2)	N5—C25—C26	115.8 (3)
C26—N6—Co1	115.5 (2)	C24—C25—C26	122.4 (3)
C3—C1—C2	118.4 (4)	N6—C26—C27	121.3 (3)
C3—C1—H1A	120.8	N6—C26—C25	115.0 (3)
C2—C1—H1A	120.8	C27—C26—C25	123.7 (3)
N1—C2—C1	123.1 (4)	C26—C27—C28	119.9 (3)
N1—C2—H2A	118.5	C26—C27—H27A	120.1
C1—C2—H2A	118.5	C28—C27—H27A	120.1
C4—C3—C1	119.7 (4)	C29—C28—C27	118.6 (4)
C4—C3—H3A	120.1	C29—C28—H28A	120.7
C1—C3—H3A	120.1	C27—C28—H28A	120.7
C3—C4—C5	119.4 (4)	C28—C29—C30	119.3 (3)
C3—C4—H4A	120.3	C28—C29—H29A	120.4
C5—C4—H4A	120.3	C30—C29—H29A	120.4
N1—C5—C4	121.3 (3)	N6—C30—C29	122.9 (3)
N1—C5—C6	116.0 (3)	N6—C30—H30A	118.6
C4—C5—C6	122.7 (3)	C29—C30—H30A	118.6
N2—C6—C7	121.9 (3)	O2—V1—O3	108.13 (15)
N2—C6—C5	115.2 (3)	O2—V1—O4	109.81 (12)
C7—C6—C5	122.9 (3)	O3—V1—O4	109.59 (13)
C6—C7—C8	119.2 (4)	O2—V1—O1	110.64 (13)
C6—C7—H7A	120.4	O3—V1—O1	107.68 (12)
C8—C7—H7A	120.4	O4—V1—O1	110.92 (11)
C9—C8—C7	119.7 (3)	O6—V2—O5	108.86 (14)
C9—C8—H8A	120.1	O6—V2—O4	109.69 (12)
C7—C8—H8A	120.1	O5—V2—O4	109.89 (13)
C8—C9—C10	118.5 (4)	O6—V2—O1^i	109.69 (12)
C8—C9—H9A	120.7	O5—V2—O1^i	111.20 (13)
C10—C9—H9A	120.7	O4—V2—O1^i	107.50 (11)
N2—C10—C9	122.8 (3)	V2^i—O1—V1	135.84 (14)
N2—C10—H10A	118.6	V2—O4—V1	155.81 (15)
C9—C10—H10A	118.6	H2C—O2W—H2D	115.9
N3—C11—C12	123.8 (4)	H3C—O3W—H3D	115.8
N3—C11—H11A	118.1	H3C—O3W—H3E	115.9
C12—C11—H11A	118.1	H3D—O3W—H3E	100.4
C11—C12—C13	118.1 (4)	H4C—O4W—H4D	115.9
C11—C12—H12A	120.9	H4C—O4W—H4E	115.9
C13—C12—H12A	120.9	H4D—O4W—H4E	123.5
C12—C13—C14	119.2 (4)	H5C—O5W—H5D	115.9
C12—C13—H13A	120.4	H5C—O5W—H5E	115.9
C14—C13—H13A	120.4	H5D—O5W—H5E	82.7
C13—C14—C15	119.8 (4)	H6C—O6W—H6D	105.6
C13—C14—H14A	120.1	H6C—O6W—H6E	110.6
C15—C14—H14A	120.1	H6D—O6W—H6E	110.6
N2—Co1—N1—C2	176.0 (3)	Co1—N2—C6—C5	−4.9 (4)
N6—Co1—N1—C2	−11.3 (3)	N1—C5—C6—N2	9.2 (4)
N4—Co1—N1—C2	126.8 (5)	C4—C5—C6—N2	−171.1 (3)
N3—Co1—N1—C2	85.0 (3)	N1—C5—C6—C7	−170.6 (3)
N5—Co1—N1—C2	−88.4 (3)	C4—C5—C6—C7	9.2 (5)
N2—Co1—N1—C5	4.8 (2)	N2—C6—C7—C8	−0.2 (5)
N6—Co1—N1—C5	177.5 (2)	C5—C6—C7—C8	179.5 (3)
N4—Co1—N1—C5	−44.4 (6)	C6—C7—C8—C9	0.9 (6)
N3—Co1—N1—C5	−86.2 (2)	C7—C8—C9—C10	−1.0 (6)
N5—Co1—N1—C5	100.4 (2)	C6—N2—C10—C9	0.2 (5)
N6—Co1—N2—C10	139.1 (5)	Co1—N2—C10—C9	−174.5 (3)
N4—Co1—N2—C10	−13.9 (3)	C8—C9—C10—N2	0.5 (6)
N3—Co1—N2—C10	−90.8 (3)	C15—N3—C11—C12	−0.9 (5)
N5—Co1—N2—C10	82.9 (3)	Co1—N3—C11—C12	179.7 (3)
N1—Co1—N2—C10	175.0 (3)	N3—C11—C12—C13	0.5 (6)
N6—Co1—N2—C6	−35.6 (6)	C11—C12—C13—C14	−0.3 (6)
N4—Co1—N2—C6	171.4 (2)	C12—C13—C14—C15	0.5 (6)
N3—Co1—N2—C6	94.5 (2)	C11—N3—C15—C14	1.1 (5)
N5—Co1—N2—C6	−91.9 (2)	Co1—N3—C15—C14	−179.4 (3)
N1—Co1—N2—C6	0.3 (2)	C11—N3—C15—C16	−179.1 (3)
N2—Co1—N3—C11	−86.7 (3)	Co1—N3—C15—C16	0.3 (4)
N6—Co1—N3—C11	83.7 (3)	C13—C14—C15—N3	−0.9 (5)
N4—Co1—N3—C11	178.6 (3)	C13—C14—C15—C16	179.3 (3)
N5—Co1—N3—C11	130.7 (6)	C20—N4—C16—C17	0.1 (5)
N1—Co1—N3—C11	−9.4 (3)	Co1—N4—C16—C17	178.6 (3)
N2—Co1—N3—C15	93.9 (2)	C20—N4—C16—C15	−179.9 (3)
N6—Co1—N3—C15	−95.7 (2)	Co1—N4—C16—C15	−1.4 (4)
N4—Co1—N3—C15	−0.8 (2)	N3—C15—C16—N4	0.7 (4)
N5—Co1—N3—C15	−48.7 (7)	C14—C15—C16—N4	−179.5 (3)
N1—Co1—N3—C15	171.2 (2)	N3—C15—C16—C17	−179.3 (3)
N2—Co1—N4—C16	−89.7 (2)	C14—C15—C16—C17	0.5 (5)
N6—Co1—N4—C16	96.0 (2)	N4—C16—C17—C18	0.4 (6)
N3—Co1—N4—C16	1.2 (2)	C15—C16—C17—C18	−179.5 (4)
N5—Co1—N4—C16	173.5 (2)	C16—C17—C18—C19	−1.0 (6)
N1—Co1—N4—C16	−41.8 (6)	C17—C18—C19—C20	1.1 (7)
N2—Co1—N4—C20	88.7 (3)	C16—N4—C20—C19	−0.1 (5)
N6—Co1—N4—C20	−85.7 (3)	Co1—N4—C20—C19	−178.4 (3)
N3—Co1—N4—C20	179.5 (3)	C18—C19—C20—N4	−0.5 (6)
N5—Co1—N4—C20	−8.2 (3)	C25—N5—C21—C22	2.4 (5)
N1—Co1—N4—C20	136.5 (5)	Co1—N5—C21—C22	−175.0 (3)
N2—Co1—N5—C21	−17.3 (3)	N5—C21—C22—C23	−2.4 (6)
N6—Co1—N5—C21	173.4 (3)	C21—C22—C23—C24	0.7 (6)
N4—Co1—N5—C21	78.5 (3)	C22—C23—C24—C25	0.8 (6)
N3—Co1—N5—C21	125.1 (6)	C21—N5—C25—C24	−0.8 (5)
N1—Co1—N5—C21	−94.7 (3)	Co1—N5—C25—C24	176.9 (3)
N2—Co1—N5—C25	165.3 (2)	C21—N5—C25—C26	−179.0 (3)
N6—Co1—N5—C25	−4.1 (2)	Co1—N5—C25—C26	−1.3 (4)
N4—Co1—N5—C25	−99.0 (2)	C23—C24—C25—N5	−0.8 (6)
N3—Co1—N5—C25	−52.4 (7)	C23—C24—C25—C26	177.3 (3)
N1—Co1—N5—C25	87.8 (2)	C30—N6—C26—C27	−1.0 (5)
N2—Co1—N6—C30	117.7 (5)	Co1—N6—C26—C27	166.4 (2)
N4—Co1—N6—C30	−89.3 (3)	C30—N6—C26—C25	179.6 (3)
N3—Co1—N6—C30	−12.0 (3)	Co1—N6—C26—C25	−13.0 (3)
N5—Co1—N6—C30	175.8 (3)	N5—C25—C26—N6	9.4 (4)
N1—Co1—N6—C30	82.8 (3)	C24—C25—C26—N6	−168.8 (3)
N2—Co1—N6—C26	−48.6 (6)	N5—C25—C26—C27	−169.9 (3)
N4—Co1—N6—C26	104.3 (2)	C24—C25—C26—C27	11.9 (5)
N3—Co1—N6—C26	−178.4 (2)	N6—C26—C27—C28	−1.3 (5)
N5—Co1—N6—C26	9.4 (2)	C25—C26—C27—C28	178.0 (3)
N1—Co1—N6—C26	−83.6 (2)	C26—C27—C28—C29	2.2 (5)
C5—N1—C2—C1	0.1 (6)	C27—C28—C29—C30	−0.8 (5)
Co1—N1—C2—C1	−170.9 (3)	C26—N6—C30—C29	2.5 (5)
C3—C1—C2—N1	1.0 (6)	Co1—N6—C30—C29	−163.6 (3)
C2—C1—C3—C4	−1.6 (6)	C28—C29—C30—N6	−1.6 (5)
C1—C3—C4—C5	1.1 (6)	O2—V1—O1—V2^i	82.3 (2)
C2—N1—C5—C4	−0.6 (5)	O3—V1—O1—V2^i	−159.7 (2)
Co1—N1—C5—C4	171.5 (3)	O4—V1—O1—V2^i	−39.8 (2)
C2—N1—C5—C6	179.1 (3)	O6—V2—O4—V1	−155.3 (4)
Co1—N1—C5—C6	−8.8 (4)	O5—V2—O4—V1	−35.6 (4)
C3—C4—C5—N1	0.0 (6)	O1^i—V2—O4—V1	85.5 (4)
C3—C4—C5—C6	−179.7 (4)	O2—V1—O4—V2	−173.8 (4)
C10—N2—C6—C7	−0.3 (5)	O3—V1—O4—V2	67.5 (4)
Co1—N2—C6—C7	174.8 (3)	O1—V1—O4—V2	−51.2 (4)
C10—N2—C6—C5	179.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O6	0.82	1.96	2.773 (3)	173
O2W—H2C···O3	0.82	2.05	2.862 (4)	169
O2W—H2D···O5	0.82	2.09	2.877 (4)	161
O3W—H3C···O5^i	0.82	2.01	2.777 (4)	157
O3W—H3D···O6W	0.82	2.00	2.767 (5)	156
O3W—H3E···O3W^ii	0.82	2.01	2.740 (6)	149
O4W—H4C···O3^iii	0.82	1.97	2.750 (4)	158
O4W—H4D···O5W	0.82	2.23	2.773 (5)	124
O4W—H4E···O6W	0.82	1.97	2.698 (5)	148
O5W—H5C···O2W^iv	0.82	2.01	2.814 (4)	165
O5W—H5D···O5W^v	0.82	2.11	2.849 (8)	149
O5W—H5E···O4W	0.82	1.96	2.773 (5)	168
O6W—H6C···O2	0.82	1.97	2.789 (4)	175
O6W—H6D···O3W	0.82	1.95	2.767 (5)	180
O6W—H6E···O4W	0.85	2.16	2.698 (5)	121

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1/2, −y+3/2, −z+1; (iv) x−1/2, y−1/2, z; (v) −x, −y+1, −z+1.