Poly[[aqua­tris­(μ-benzene-1,4-dicarboxyl­ato)tricobalt(II)] methanol monosolvate monohydrate]

Abstract

The asymmetric unit of the title compound, {[Co₃(C₈H₄O₄)₃(H₂O)]·CH₃OH·H₂O}_n, consists of four crystallographically independent Co cations, four benzene-1,4-dicarboxyl­ate (bdc) anions, two water and one methanol solvent mol­ecule. Two of the Co cations and two of the bdc anions are located on centres of inversion, whereas all other atoms are located in general positions. In the crystal, two Co atoms are only fourfold coordinated by three O atoms from three bdc ligands and by one O atom from one coordinated water mol­ecule, while a third Co atom is coordinated by four O atoms from four bdc ligands within a strongly distorted tetra­hedral geometry. The other two Co cations are octa­hedrally coordinated by six O atoms from six bdc anions. The Co cations are linked by the bdc anions into a three-dimensional framework. From this arrangement, cavities are formed in which additional methanol and water mol­ecules are embedded.

Related literature

For related structures, see: Rosi et al. (2005 ▶); Devic et al. (2005 ▶); Humphrey et al. (2007 ▶); Luo et al. (2007 ▶, 2008 ▶). For general background to benzene-1,4-dicarb­oxy­lic acid (H₂bdc), see: Férey et al. (2005 ▶); Rosi et al. (2003 ▶). For background to metal-organic frameworks (MOFs), see: Long & Yaghi (2009 ▶).

Experimental

Crystal data

• [Co₃(C₈H₄O₄)₃(H₂O)]·CH₄O·H₂O

• M _r = 737.20

• Triclinic,

• a = 9.8456 (11) Å

• b = 12.0753 (15) Å

• c = 13.0039 (16) Å

• α = 91.842 (2)°

• β = 100.925 (1)°

• γ = 101.745 (1)°

• V = 1482.2 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 1.73 mm⁻¹

• T = 291 K

• 0.30 × 0.26 × 0.24 mm

Data collection

• Bruker SMART APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.682, T _max = 0.746

• 11744 measured reflections

• 5751 independent reflections

• 4241 reflections with I > 2σ(I)

• R _int = 0.031

Refinement

• R[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 0.110

• S = 1.04

• 5751 reflections

• 392 parameters

• H-atom parameters constrained

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.70 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

Recently, research on metal-organic frameworks (MOFs) has become of increasing interest (Long et al., 2009). In this context compounds based on dicarboxylate ligands are of special importance (Férey et al., 2005; Rosi et al., 2003). In our own investigations we tried to prepare new MOFs based on benzene-1,4-dicarboxylic acid (H₂bdc) and amines as ligands. Within this project we have reacted CoCl₂.6H₂O with H₂bdc and N,N'-bis(4-pyridylmethylidine)-1,4-phenylenediamine and we have obtained crystals of the title compound by accident.

The title compound is a three-dimensional framework the form hex type (Rosi et al., 2005) built from Co cations that are linked by bdc anions. From this arrangement cavities are formed, that are filled with additional uncoordinated methanol and water molecules. Altogether there are four crystallographically independent Co cations of which two (Co2 and Co4) are located on centers of inversion. Co1 is coordinated by three oxygen atoms from three bdc ligands and one oxygen atom from one coordinated water molecule within a strongly distorted tetrahedron. Co3 is also tetrahedrally coordinated but connected only to four oxygen atoms from four bdc ligands. In contrast Co2 and Co4 are 6-fold coordinated by six oxygen atoms from bdc anions within slightly distorted octahedra. Related complexes have been reported recently (Devic et al., 2005; Humphrey et al., 2007; Luo et al., 2007; Luo et al., 2008).

Experimental

A mixture of CoCl₂.6H₂O (0.0238 g, 0.1 mmol), benzene-1,4-dicarboxylic acid (0.0166 g, 0.1 mmol), N,N'-bis(4-pyridylmethylidine)-1,4-phenylenediamine (0.0290 g, 0.1 mmol) combined with 5 ml mixed solvent (DMF:CH₃OH = 1:1) was stirred for 20 min at room temperature. Afterwards the solution was heated in a 25 ml Teflon-lined stainless-steel vessel at 140 ^oC for 72 h under autogenous pressure. Slow cooling of the resulting solution to room temperature at the rate of 10 ^oC.h^-1 afforded purple block-shaped crystals suitable for single-crystal X-ray structure analysis. Yield based on CoCl₂.6H₂O: 35%.

Refinement

All non-hydrogen atoms were refined with anisotropic thermal parameters. The C-H H atoms were calculated in idealized positions with C—H = 0.95 or 0.96 Å and included in the refinement in a riding mode with U_iso for H assigned as 1.2 or 1.5 times U_eq of the attached atoms. The H atoms bound to oxygen atoms from coordinated and crystallized water molecules were located from difference maps and refined as riding, with O - H restraint (O - H = 0.96 or 0.85 Å), and with U_iso(H) = 1.2U_eq(O).

Figures

Fig. 1.

ORTEP diagram of the title compound. Displacement ellipsoids are drawn at 30% probability level. Hydrogen atoms have been omitted for clarity. Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 3, -y + 2, -z; (iii) -x + 1, -y + 1, -z + 1; (iv) x, y + 1, z - 1; (v) -x + 2, -y + 2, -z + 1; (vi) -x + 2, -y + 1, -z + 1; (vii) -x + 2, -y + 2, -z.

Crystal data

[Co3(C8H4O4)3(H2O)]·CH4O·H2O	Z = 2
Mr = 737.20	F(000) = 742
Triclinic, P1	Dx = 1.652 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8456 (11) Å	Cell parameters from 3571 reflections
b = 12.0753 (15) Å	θ = 2.2–24.1°
c = 13.0039 (16) Å	µ = 1.73 mm−1
α = 91.842 (2)°	T = 291 K
β = 100.925 (1)°	Block, purple
γ = 101.745 (1)°	0.30 × 0.26 × 0.24 mm
V = 1482.2 (3) Å3

Data collection

Bruker SMART APEX CCD diffractometer	5751 independent reflections
Radiation source: sealed tube	4241 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→12
Tmin = 0.682, Tmax = 0.746	k = −14→14
11744 measured reflections	l = −15→16

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.05P)2 + 1.22P] where P = (Fo2 + 2Fc2)/3
5751 reflections	(Δ/σ)max < 0.001
392 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.70 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
C1	0.7655 (4)	0.4662 (3)	0.7910 (3)	0.0345 (9)
C2	0.7907 (5)	0.3680 (4)	0.7456 (4)	0.0454 (11)
H2	0.7628	0.3508	0.6719	0.054*
C3	0.8574 (5)	0.2946 (4)	0.8090 (4)	0.0419 (10)
H3	0.8717	0.2262	0.7790	0.050*
C4	0.9021 (5)	0.3234 (3)	0.9161 (3)	0.0398 (10)
C5	0.8818 (5)	0.4247 (4)	0.9588 (4)	0.0485 (12)
H5	0.9157	0.4461	1.0315	0.058*
C6	0.8129 (5)	0.4934 (4)	0.8958 (3)	0.0426 (10)
H6	0.7980	0.5615	0.9261	0.051*
C7	0.6950 (5)	0.5449 (4)	0.7247 (4)	0.0412 (10)
C8	0.9731 (5)	0.2503 (3)	0.9811 (4)	0.0422 (11)
C9	0.7203 (4)	0.8267 (3)	0.4169 (3)	0.0301 (8)
C10	0.6962 (5)	0.7946 (4)	0.3063 (4)	0.0505 (12)
H10	0.6323	0.7266	0.2758	0.061*
C11	0.7716 (5)	0.8688 (4)	0.2457 (4)	0.0429 (10)
H11	0.7599	0.8486	0.1728	0.052*
C12	0.8616 (5)	0.9694 (3)	0.2872 (3)	0.0400 (10)
C13	0.8770 (5)	1.0004 (4)	0.3927 (4)	0.0501 (12)
H13	0.9324	1.0721	0.4222	0.060*
C14	0.8078 (5)	0.9223 (4)	0.4566 (3)	0.0421 (11)
H14	0.8257	0.9401	0.5302	0.051*
C15	0.6447 (4)	0.7483 (3)	0.4814 (3)	0.0317 (8)
C16	0.9373 (4)	1.0442 (4)	0.2203 (3)	0.0375 (9)
C17	0.2859 (4)	0.6297 (4)	0.5711 (3)	0.0371 (10)
C18	0.1060 (5)	0.4418 (4)	0.5392 (4)	0.0426 (10)
H18	0.1803	0.4042	0.5644	0.051*
C19	0.1364 (4)	0.5612 (4)	0.5314 (3)	0.0356 (9)
C20	0.0241 (4)	0.6157 (4)	0.4882 (3)	0.0388 (10)
H20	0.0448	0.6948	0.4795	0.047*
C21	1.3134 (4)	1.1321 (4)	0.0668 (4)	0.0406 (10)
C22	1.5397 (5)	1.1132 (4)	−0.0081 (3)	0.0443 (11)
H22	1.5718	1.1927	−0.0099	0.053*
C23	1.4218 (5)	1.0740 (3)	0.0374 (3)	0.0378 (9)
C24	1.3909 (5)	0.9566 (4)	0.0493 (4)	0.0418 (10)
H24	1.3199	0.9262	0.0871	0.050*
C25	0.2871 (5)	0.4940 (4)	0.8243 (4)	0.0463 (11)
H25A	0.1955	0.4495	0.8330	0.069*
H25C	0.3313	0.4480	0.7826	0.069*
H25D	0.2728	0.5619	0.7881	0.069*
Co1	0.53756 (6)	0.71571 (5)	0.67841 (4)	0.03287 (15)
Co2	0.5000	0.5000	0.5000	0.03250 (18)
Co3	1.15981 (5)	1.21536 (4)	0.17863 (4)	0.02938 (14)
Co4	1.0000	1.0000	0.0000	0.03193 (18)
O1	0.6831 (3)	0.6278 (3)	0.7537 (2)	0.0465 (8)
O2	0.6588 (3)	0.5129 (3)	0.6183 (2)	0.0415 (7)
O3	0.9700 (3)	0.1490 (2)	0.9415 (2)	0.0377 (7)
O4	1.0326 (3)	0.2841 (2)	1.0748 (2)	0.0410 (7)
O5	0.6481 (3)	0.7837 (3)	0.5886 (3)	0.0476 (8)
O6	0.5728 (3)	0.6495 (2)	0.4424 (2)	0.0375 (7)
O7	0.9028 (3)	1.0201 (2)	0.1217 (2)	0.0352 (6)
O8	1.0366 (3)	1.1244 (3)	0.2642 (2)	0.0488 (8)
O9	0.3832 (3)	0.5818 (2)	0.6010 (2)	0.0344 (6)
O10	0.3048 (3)	0.7359 (3)	0.5713 (3)	0.0472 (8)
O11	1.2079 (3)	1.0796 (2)	0.0968 (2)	0.0378 (7)
O12	1.3470 (3)	1.2378 (3)	0.0664 (2)	0.0431 (7)
O13	0.3793 (3)	0.5276 (3)	0.9276 (2)	0.0409 (7)
H15B	0.4504	0.5936	0.9225	0.049*
O1W	0.4003 (3)	0.7587 (3)	0.7928 (3)	0.0458 (7)
H1X	0.3246	0.7899	0.7555	0.055*
H1Y	0.4577	0.8130	0.8474	0.055*
O2W	0.6664 (4)	0.9904 (3)	0.6639 (3)	0.0574 (9)
H2X	0.6605	0.9232	0.6394	0.069*
H2Y	0.7051	0.9975	0.7287	0.069*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.035 (2)	0.0287 (19)	0.037 (2)	−0.0018 (16)	0.0105 (17)	0.0053 (16)
C2	0.052 (3)	0.040 (2)	0.049 (3)	0.021 (2)	0.007 (2)	0.010 (2)
C3	0.043 (2)	0.040 (2)	0.042 (2)	0.0108 (19)	0.0044 (19)	−0.0060 (19)
C4	0.043 (2)	0.0248 (19)	0.039 (2)	0.0000 (17)	−0.0150 (19)	0.0038 (17)
C5	0.042 (3)	0.049 (3)	0.051 (3)	0.015 (2)	−0.006 (2)	0.009 (2)
C6	0.046 (3)	0.041 (2)	0.039 (2)	0.014 (2)	−0.001 (2)	0.0028 (19)
C7	0.048 (3)	0.036 (2)	0.039 (2)	0.0143 (19)	−0.0013 (19)	0.0020 (19)
C8	0.042 (2)	0.027 (2)	0.043 (2)	−0.0058 (17)	−0.0123 (19)	0.0003 (18)
C9	0.038 (2)	0.0307 (19)	0.0259 (19)	0.0086 (16)	0.0154 (16)	0.0076 (15)
C10	0.046 (3)	0.049 (3)	0.047 (3)	−0.014 (2)	0.012 (2)	−0.009 (2)
C11	0.039 (2)	0.043 (2)	0.042 (2)	−0.0065 (19)	0.0136 (19)	0.0080 (19)
C12	0.052 (3)	0.030 (2)	0.038 (2)	0.0021 (18)	0.014 (2)	0.0051 (17)
C13	0.039 (3)	0.058 (3)	0.044 (3)	−0.016 (2)	0.017 (2)	−0.006 (2)
C14	0.045 (2)	0.047 (2)	0.029 (2)	−0.0140 (19)	0.0191 (18)	−0.0087 (18)
C15	0.031 (2)	0.033 (2)	0.035 (2)	0.0109 (17)	0.0111 (17)	0.0033 (16)
C16	0.029 (2)	0.043 (2)	0.037 (2)	0.0043 (18)	0.0010 (17)	0.0074 (18)
C17	0.024 (2)	0.047 (2)	0.042 (2)	0.0131 (18)	0.0088 (17)	−0.0194 (19)
C18	0.039 (2)	0.050 (3)	0.040 (2)	0.011 (2)	0.0109 (19)	−0.009 (2)
C19	0.0220 (19)	0.047 (2)	0.040 (2)	0.0097 (17)	0.0076 (16)	0.0106 (18)
C20	0.027 (2)	0.047 (2)	0.045 (2)	0.0127 (18)	0.0089 (18)	0.010 (2)
C21	0.021 (2)	0.046 (3)	0.048 (3)	0.0071 (18)	−0.0085 (18)	−0.012 (2)
C22	0.047 (3)	0.038 (2)	0.040 (2)	−0.009 (2)	0.014 (2)	−0.0141 (19)
C23	0.049 (3)	0.031 (2)	0.039 (2)	0.0132 (18)	0.0160 (19)	0.0091 (17)
C24	0.039 (2)	0.046 (3)	0.041 (2)	0.005 (2)	0.0135 (19)	0.007 (2)
C25	0.052 (3)	0.050 (3)	0.042 (3)	0.020 (2)	0.011 (2)	0.017 (2)
Co1	0.0347 (3)	0.0324 (3)	0.0326 (3)	0.0089 (2)	0.0080 (2)	−0.0003 (2)
Co2	0.0330 (4)	0.0316 (4)	0.0325 (4)	0.0079 (3)	0.0049 (3)	−0.0009 (3)
Co3	0.0267 (3)	0.0323 (3)	0.0271 (3)	0.0056 (2)	0.0015 (2)	0.0005 (2)
Co4	0.0336 (4)	0.0275 (4)	0.0332 (4)	0.0048 (3)	0.0052 (3)	0.0004 (3)
O1	0.0524 (19)	0.0331 (17)	0.0452 (18)	0.0145 (14)	−0.0167 (15)	−0.0057 (14)
O2	0.0440 (17)	0.0429 (17)	0.0382 (16)	0.0121 (14)	0.0057 (13)	0.0069 (13)
O3	0.0389 (16)	0.0433 (16)	0.0391 (16)	0.0201 (13)	0.0150 (13)	0.0105 (13)
O4	0.0444 (17)	0.0395 (16)	0.0288 (15)	0.0059 (13)	−0.0132 (13)	−0.0077 (12)
O5	0.0482 (18)	0.0426 (17)	0.0477 (18)	−0.0097 (14)	0.0222 (15)	−0.0115 (14)
O6	0.0356 (15)	0.0306 (15)	0.0393 (16)	0.0071 (12)	−0.0088 (12)	−0.0015 (12)
O7	0.0272 (14)	0.0441 (16)	0.0321 (16)	0.0020 (12)	0.0061 (12)	0.0048 (12)
O8	0.0491 (19)	0.0430 (18)	0.0435 (18)	−0.0162 (15)	0.0123 (15)	−0.0080 (14)
O9	0.0275 (14)	0.0438 (16)	0.0333 (15)	0.0138 (12)	0.0038 (11)	−0.0045 (12)
O10	0.0519 (19)	0.0427 (18)	0.0460 (18)	0.0149 (15)	0.0051 (15)	−0.0127 (14)
O11	0.0399 (17)	0.0416 (16)	0.0320 (15)	0.0062 (13)	0.0105 (13)	−0.0001 (12)
O12	0.0432 (17)	0.0422 (17)	0.0427 (17)	0.0040 (14)	0.0142 (14)	−0.0160 (14)
O13	0.0421 (17)	0.0412 (17)	0.0441 (17)	0.0105 (13)	0.0165 (14)	0.0129 (13)
O1W	0.0454 (18)	0.0419 (17)	0.0494 (18)	0.0047 (14)	0.0156 (14)	−0.0145 (14)
O2W	0.058 (2)	0.051 (2)	0.053 (2)	−0.0121 (16)	0.0132 (17)	−0.0059 (16)

Geometric parameters (Å, °)

C1—C6	1.360 (6)	C21—O11	1.239 (5)
C1—C2	1.395 (6)	C21—O12	1.252 (5)
C1—C7	1.491 (6)	C21—C23	1.489 (6)
C2—C3	1.405 (6)	C22—C24ii	1.345 (6)
C2—H2	0.9500	C22—C23	1.406 (6)
C3—C4	1.388 (6)	C22—H22	0.9500
C3—H3	0.9500	C23—C24	1.408 (6)
C4—C5	1.393 (6)	C24—C22ii	1.345 (6)
C4—C8	1.435 (6)	C24—H24	0.9500
C5—C6	1.372 (6)	C25—O13	1.465 (5)
C5—H5	0.9500	C25—H25A	0.9800
C6—H6	0.9500	C25—H25C	0.9800
C7—O1	1.095 (5)	C25—H25D	0.9800
C7—O2	1.383 (5)	Co1—O5	1.845 (3)
C8—O4	1.262 (5)	Co1—O9	2.062 (3)
C8—O3	1.305 (5)	Co1—O1	2.072 (3)
C9—C14	1.315 (6)	Co1—O1W	2.304 (3)
C9—C10	1.440 (6)	Co2—O2	1.952 (3)
C9—C15	1.468 (5)	Co2—O2iii	1.952 (3)
C10—C11	1.404 (6)	Co2—O6	2.024 (3)
C10—H10	0.9500	Co2—O6iii	2.024 (3)
C11—C12	1.376 (6)	Co2—O9	2.230 (3)
C11—H11	0.9500	Co2—O9iii	2.230 (3)
C12—C13	1.381 (6)	Co3—O4iv	1.984 (3)
C12—C16	1.467 (6)	Co3—O8	1.990 (3)
C13—C14	1.431 (6)	Co3—O11	2.107 (3)
C13—H13	0.9500	Co3—O1v	2.222 (3)
C14—H14	0.9500	Co4—O3iv	2.030 (3)
C15—O6	1.289 (5)	Co4—O3vi	2.030 (3)
C15—O5	1.437 (5)	Co4—O7	2.030 (3)
C16—O8	1.260 (5)	Co4—O7vii	2.030 (3)
C16—O7	1.271 (5)	Co4—O11	2.201 (3)
C17—O9	1.226 (5)	Co4—O11vii	2.201 (3)
C17—O10	1.258 (5)	O1—Co3v	2.222 (3)
C17—C19	1.519 (6)	O3—Co4viii	2.030 (3)
C18—C20i	1.304 (6)	O4—Co3viii	1.984 (3)
C18—C19	1.422 (6)	O13—H15B	0.9600
C18—H18	0.9500	O1W—H1X	0.9601
C19—C20	1.434 (5)	O1W—H1Y	0.9600
C20—C18i	1.304 (6)	O2W—H2X	0.8501
C20—H20	0.9500	O2W—H2Y	0.8500
C6—C1—C2	119.5 (4)	C23—C24—H24	119.4
C6—C1—C7	119.8 (4)	O13—C25—H25A	109.5
C2—C1—C7	120.6 (4)	O13—C25—H25C	109.5
C1—C2—C3	120.0 (4)	H25A—C25—H25C	109.5
C1—C2—H2	120.0	O13—C25—H25D	109.5
C3—C2—H2	120.0	H25A—C25—H25D	109.5
C4—C3—C2	119.1 (4)	H25C—C25—H25D	109.5
C4—C3—H3	120.5	O5—Co1—O9	110.87 (13)
C2—C3—H3	120.5	O5—Co1—O1	96.16 (16)
C3—C4—C5	119.8 (4)	O9—Co1—O1	99.86 (11)
C3—C4—C8	119.5 (4)	O5—Co1—O1W	140.91 (13)
C5—C4—C8	120.6 (4)	O9—Co1—O1W	93.65 (11)
C6—C5—C4	120.0 (4)	O1—Co1—O1W	109.49 (14)
C6—C5—H5	120.0	O2—Co2—O2iii	180.000 (1)
C4—C5—H5	120.0	O2—Co2—O6	96.10 (12)
C1—C6—C5	121.5 (4)	O2iii—Co2—O6	83.90 (12)
C1—C6—H6	119.3	O2—Co2—O6iii	83.90 (12)
C5—C6—H6	119.3	O2iii—Co2—O6iii	96.10 (12)
O1—C7—O2	120.2 (4)	O6—Co2—O6iii	180.0
O1—C7—C1	124.2 (4)	O2—Co2—O9	90.15 (11)
O2—C7—C1	115.2 (4)	O2iii—Co2—O9	89.85 (11)
O4—C8—O3	122.1 (4)	O6—Co2—O9	91.77 (11)
O4—C8—C4	119.7 (4)	O6iii—Co2—O9	88.23 (11)
O3—C8—C4	118.2 (4)	O2—Co2—O9iii	89.85 (11)
C14—C9—C10	120.2 (4)	O2iii—Co2—O9iii	90.15 (11)
C14—C9—C15	122.6 (4)	O6—Co2—O9iii	88.23 (11)
C10—C9—C15	117.2 (4)	O6iii—Co2—O9iii	91.77 (11)
C11—C10—C9	116.8 (4)	O9—Co2—O9iii	180.000 (1)
C11—C10—H10	121.6	O4iv—Co3—O8	106.09 (14)
C9—C10—H10	121.6	O4iv—Co3—O11	106.51 (11)
C12—C11—C10	122.8 (4)	O8—Co3—O11	97.95 (13)
C12—C11—H11	118.6	O4iv—Co3—O1v	98.73 (11)
C10—C11—H11	118.6	O8—Co3—O1v	121.70 (13)
C11—C12—C13	118.9 (4)	O11—Co3—O1v	124.18 (12)
C11—C12—C16	120.6 (4)	O3iv—Co4—O3vi	180.00 (6)
C13—C12—C16	120.4 (4)	O3iv—Co4—O7	93.55 (11)
C12—C13—C14	118.7 (4)	O3vi—Co4—O7	86.45 (11)
C12—C13—H13	120.7	O3iv—Co4—O7vii	86.45 (11)
C14—C13—H13	120.7	O3vi—Co4—O7vii	93.55 (11)
C9—C14—C13	122.3 (4)	O7—Co4—O7vii	180.000 (1)
C9—C14—H14	118.8	O3iv—Co4—O11	92.68 (12)
C13—C14—H14	118.8	O3vi—Co4—O11	87.32 (12)
O6—C15—O5	119.8 (3)	O7—Co4—O11	91.18 (11)
O6—C15—C9	120.9 (4)	O7vii—Co4—O11	88.82 (11)
O5—C15—C9	119.3 (3)	O3iv—Co4—O11vii	87.32 (12)
O8—C16—O7	124.3 (4)	O3vi—Co4—O11vii	92.68 (12)
O8—C16—C12	118.2 (4)	O7—Co4—O11vii	88.82 (11)
O7—C16—C12	117.5 (4)	O7vii—Co4—O11vii	91.18 (10)
O9—C17—O10	122.1 (4)	O11—Co4—O11vii	180.0
O9—C17—C19	120.4 (4)	C7—O1—Co1	124.3 (3)
O10—C17—C19	117.4 (4)	C7—O1—Co3v	132.2 (3)
C20i—C18—C19	119.8 (4)	Co1—O1—Co3v	93.67 (12)
C20i—C18—H18	120.1	C7—O2—Co2	140.1 (3)
C19—C18—H18	120.1	C8—O3—Co4viii	135.7 (3)
C18—C19—C20	119.3 (4)	C8—O4—Co3viii	130.1 (3)
C18—C19—C17	119.9 (4)	C15—O5—Co1	128.3 (3)
C20—C19—C17	120.8 (4)	C15—O6—Co2	136.0 (3)
C18i—C20—C19	120.8 (4)	C16—O7—Co4	138.1 (3)
C18i—C20—H20	119.6	C16—O8—Co3	119.8 (3)
C19—C20—H20	119.6	C17—O9—Co1	100.9 (3)
O11—C21—O12	124.7 (4)	C17—O9—Co2	126.7 (3)
O11—C21—C23	122.0 (4)	Co1—O9—Co2	102.39 (11)
O12—C21—C23	113.0 (4)	C21—O11—Co3	98.8 (3)
C24ii—C22—C23	123.1 (4)	C21—O11—Co4	127.7 (3)
C24ii—C22—H22	118.5	Co3—O11—Co4	101.90 (12)
C23—C22—H22	118.5	C25—O13—H15B	109.3
C22—C23—C24	115.3 (4)	Co1—O1W—H1X	109.6
C22—C23—C21	131.7 (4)	Co1—O1W—H1Y	109.4
C24—C23—C21	112.7 (4)	H1X—O1W—H1Y	109.5
C22ii—C24—C23	121.1 (4)	H2X—O2W—H2Y	109.5
C22ii—C24—H24	119.4
C6—C1—C2—C3	3.6 (7)	O6iii—Co2—O2—C7	−82.0 (4)
C7—C1—C2—C3	179.9 (4)	O9—Co2—O2—C7	6.3 (4)
C1—C2—C3—C4	−2.4 (7)	O9iii—Co2—O2—C7	−173.7 (4)
C2—C3—C4—C5	−0.7 (7)	O4—C8—O3—Co4viii	17.9 (7)
C2—C3—C4—C8	−178.6 (4)	C4—C8—O3—Co4viii	−160.1 (3)
C3—C4—C5—C6	2.5 (7)	O3—C8—O4—Co3viii	11.3 (7)
C8—C4—C5—C6	−179.6 (5)	C4—C8—O4—Co3viii	−170.8 (3)
C2—C1—C6—C5	−1.8 (7)	O6—C15—O5—Co1	−11.2 (5)
C7—C1—C6—C5	−178.1 (4)	C9—C15—O5—Co1	167.2 (3)
C4—C5—C6—C1	−1.3 (8)	O9—Co1—O5—C15	−5.8 (4)
C6—C1—C7—O1	3.7 (8)	O1—Co1—O5—C15	97.2 (3)
C2—C1—C7—O1	−172.6 (5)	O1W—Co1—O5—C15	−131.1 (3)
C6—C1—C7—O2	176.1 (4)	O5—C15—O6—Co2	−22.8 (6)
C2—C1—C7—O2	−0.2 (6)	C9—C15—O6—Co2	158.9 (3)
C3—C4—C8—O4	169.3 (4)	O2—Co2—O6—C15	−33.7 (4)
C5—C4—C8—O4	−8.6 (7)	O2iii—Co2—O6—C15	146.3 (4)
C3—C4—C8—O3	−12.7 (7)	O9—Co2—O6—C15	56.6 (4)
C5—C4—C8—O3	169.4 (4)	O9iii—Co2—O6—C15	−123.4 (4)
C14—C9—C10—C11	1.0 (7)	O8—C16—O7—Co4	46.4 (7)
C15—C9—C10—C11	−178.5 (4)	C12—C16—O7—Co4	−129.9 (4)
C9—C10—C11—C12	−1.9 (7)	O3iv—Co4—O7—C16	−106.4 (4)
C10—C11—C12—C13	−1.2 (7)	O3vi—Co4—O7—C16	73.6 (4)
C10—C11—C12—C16	−179.7 (4)	O11—Co4—O7—C16	−13.6 (4)
C11—C12—C13—C14	5.1 (7)	O11vii—Co4—O7—C16	166.4 (4)
C16—C12—C13—C14	−176.4 (4)	O7—C16—O8—Co3	−4.6 (6)
C10—C9—C14—C13	3.0 (7)	C12—C16—O8—Co3	171.7 (3)
C15—C9—C14—C13	−177.5 (4)	O4iv—Co3—O8—C16	60.0 (4)
C12—C13—C14—C9	−6.1 (8)	O11—Co3—O8—C16	−49.8 (4)
C14—C9—C15—O6	−171.9 (4)	O1v—Co3—O8—C16	171.3 (3)
C10—C9—C15—O6	7.7 (6)	O10—C17—O9—Co1	14.7 (5)
C14—C9—C15—O5	9.8 (6)	C19—C17—O9—Co1	−165.7 (3)
C10—C9—C15—O5	−170.7 (4)	O10—C17—O9—Co2	−99.9 (4)
C11—C12—C16—O8	−167.5 (4)	C19—C17—O9—Co2	79.7 (5)
C13—C12—C16—O8	14.1 (7)	O5—Co1—O9—C17	−90.8 (3)
C11—C12—C16—O7	9.0 (6)	O1—Co1—O9—C17	168.6 (3)
C13—C12—C16—O7	−169.4 (4)	O1W—Co1—O9—C17	58.1 (3)
C20i—C18—C19—C20	−3.2 (7)	O5—Co1—O9—Co2	40.87 (17)
C20i—C18—C19—C17	175.3 (4)	O1—Co1—O9—Co2	−59.66 (15)
O9—C17—C19—C18	6.7 (6)	O1W—Co1—O9—Co2	−170.18 (12)
O10—C17—C19—C18	−173.7 (4)	O2—Co2—O9—C17	158.8 (4)
O9—C17—C19—C20	−174.8 (4)	O2iii—Co2—O9—C17	−21.2 (4)
O10—C17—C19—C20	4.8 (6)	O6—Co2—O9—C17	62.6 (4)
C18—C19—C20—C18i	3.2 (7)	O6iii—Co2—O9—C17	−117.4 (4)
C17—C19—C20—C18i	−175.3 (4)	O2—Co2—O9—Co1	44.79 (13)
C24ii—C22—C23—C24	7.7 (8)	O2iii—Co2—O9—Co1	−135.21 (13)
C24ii—C22—C23—C21	−165.6 (5)	O6—Co2—O9—Co1	−51.32 (12)
O11—C21—C23—C22	172.5 (5)	O6iii—Co2—O9—Co1	128.68 (12)
O12—C21—C23—C22	−13.3 (7)	O12—C21—O11—Co3	−15.7 (5)
O11—C21—C23—C24	−0.9 (6)	C23—C21—O11—Co3	157.8 (4)
O12—C21—C23—C24	173.4 (4)	O12—C21—O11—Co4	96.9 (5)
C22—C23—C24—C22ii	−7.5 (7)	C23—C21—O11—Co4	−89.6 (5)
C21—C23—C24—C22ii	167.0 (4)	O4iv—Co3—O11—C21	88.6 (3)
O2—C7—O1—Co1	27.2 (7)	O8—Co3—O11—C21	−161.9 (3)
C1—C7—O1—Co1	−160.8 (3)	O1v—Co3—O11—C21	−24.5 (3)
O2—C7—O1—Co3v	−109.1 (4)	O4iv—Co3—O11—Co4	−43.08 (15)
C1—C7—O1—Co3v	63.0 (7)	O8—Co3—O11—Co4	66.39 (14)
O5—Co1—O1—C7	−84.9 (5)	O1v—Co3—O11—Co4	−156.19 (11)
O9—Co1—O1—C7	27.6 (5)	O3iv—Co4—O11—C21	−58.9 (4)
O1W—Co1—O1—C7	125.1 (4)	O3vi—Co4—O11—C21	121.1 (4)
O5—Co1—O1—Co3v	64.22 (14)	O7—Co4—O11—C21	−152.6 (4)
O9—Co1—O1—Co3v	176.70 (12)	O7vii—Co4—O11—C21	27.4 (4)
O1W—Co1—O1—Co3v	−85.82 (14)	O3iv—Co4—O11—Co3	52.20 (13)
O1—C7—O2—Co2	−53.0 (7)	O3vi—Co4—O11—Co3	−127.80 (13)
C1—C7—O2—Co2	134.3 (4)	O7—Co4—O11—Co3	−41.41 (13)
O6—Co2—O2—C7	98.0 (4)	O7vii—Co4—O11—Co3	138.59 (13)

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