A novel cobalt(II) coordination polymer containing the fumarate anion and o-phenanthroline

The self-assembly of three crystallographically distinct fumar­ate ions, two unique cobalt(II) ions and two unique o-phen­;anthroline mol­ecules results in a two-dimensional polymeric structure with the formula [Co₂(C₄H₂O₄)₂(C₁₂H₈N₂)₂]_n, namely di-[mu]-fumatato-bis(o-phenanthroline)­dicobalt(II). The Co atoms are at the nodes of a two-dimensional array linked by coordinated fumarate ligands. Each Co atom is coordinated in a distorted octahedral manner to four fumarate O atoms and two N atoms from the chelating phenanthroline ligands.

S1. Comment

The coordination chemistry of polycarboxylic acids has been studied widely (Rochon & Massarweh, 2001). Polycarboxylic acids such as fumaric and maleic acid are capable of forming one-, two- or three-dimensional infinite connections between cations and anions (Young et al., 1998; Ma et al., 1993), thereby forming chain structures, layered compounds or three-dimensional frameworks. The reported metal–fumarate complexes indicate that there may be a wide variety of structural and chemical properties depending on the nature of cations employed. To our knowledge, only a few metal–fumarate complexes with other neutral ligands have been reported (for example, Mukherjee et al., 2001; Devereux et al., 2000; Charpin et al., 1987). The incorporation of a second organic ligand into metal–fumarate phases provides a powerful method for structural modification and synthesis of novel organic–inorganic hybrid materials. Organic components have been used as structure-directing reagents in a wide range of materials, including zeolites and mesoporous materials of the MCM-41 class (Zapf et al., 1997). We report here the preparation and crystal structure of a new cobalt(II)–fumarate (fum) complex with o-phenanthroline (phen), namely poly[Co₂(fum)₂(phen)₂], (I).

The structure contains three crystallographically distinct fumarate ions (F, F' and F''), two unique cobalt(II) ions and two unique o-phenanthroline molecules (Fig. 1). Ions F and F' and the two cobalt(II) ions are linked into chains, with the sequence (···FCo₂F'Co₂···), parallel to a. The bridging carboxylate groups give rise to eight-membered rings (Figs. 2 and 3). These chains are cross-linked by the third fumarate ion (F''), which forms four-membered chelate rings with a Co^II atom at each end, thus completing a two-dimensional polymeric arrangement containing both eight- and 28-membered rings. The trans-ring Co···Co distance is 4.430 (2) Å in the eight-membered ring, while the Co···Co edge lengths are 7.918 (2) and 8.728 (2) Å for the 28-membered ring. One o-phenantholine chelating ligand completes a distorted octahedral coordination environment about each unique Co^II atom. The o-phenanthroline ligands fill the space formed by the 28-membered rings and contribute some additional stability to the net via π–π interactions (interplanar distances are 3.40 and 3.59 Å). The average Co—N distance of 2.130 Å is similar to that of other cobalt(II) complexes with o-phenanthroline (Yin & Jiang, 2001), and the Co—O (fumarate) distances range from 2.023 to 2.184 Å (Table 1).

The cobalt(II) cations are thus bridged by fumarate anions to form an infinite two-dimensional polymeric structure. Many two-dimensional coordination polymers have been reported, but examples containing two kinds of circuits are rarely seen (Dai et al., 2002). The structure of (I) is clearly different from that of the cobalt(II)–fumarate complex reported by Gupta & Sinha (1978), in which the Co^II atom is six-coordinated by four water molecules and two carboxylate O atoms from the fumarate anion. It can be seen that the incorporation of an o-phenanthroline ligand into cobalt(II)–fumarate phases provides a powerful method for structural modification and synthesis of novel structures. Interpenetration often occurs in compounds with two-dimensional polymeric structures (Ma et al., 2000), but in (I), interpenetration does not occur. We believe that the o-phenanthroline molecules prevent self-interpenetration by occupying the large voids in network structures.

We conclude that the incorporation of an o-phenanthroline ligand into cobalt(II)–fumarate phases provides a powerful method for the structural modification and synthesis of novel architectures.

S2. Experimental

A mixture of fumaric acid (0.116 g, 1 mmol) and NaOH (0.080 g, 2 mmol) in water (10 ml) was added with constant stirring to a solution of CoCl₂·6H₂O (0.237 g, 1 mmol) in water (10 ml). o-Phenanthroline (0.198 g, 1 mmol) was added to the solution with stirring. Purple crystals of (I) were obtained from the solution after it had stood at room temperature for several days (68% yield based on Co). Analysis calculated for C₃₂H₂0N₄O₈Co₂: C 54.36, H 2.83, N 7.93; found: C 54.53, H 2.68, N 8.03%. IR (cm⁻¹, KBr): 3439(versus), 3063(w), 2171(w), 1600(versus), 1555(s), 1515(m), 1454(m), 1426(s), 1375(m), 1199(w), 1146(w), 1107(w), 985(w), 856(w), 801(w), 729(m), 696(m), 679(w).

S3. Refinement

All H atoms attached to C atoms were positioned geometrically and refined as riding atoms, with C—H distance of 0.93 Å and U_iso(H) values of 1.2U_eq(C).

Computing details

Data collection: PROCESS-AUTO; cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990).

Figures

	Fig. 1. A view of the local coordination of the Co^II atoms, with the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level. [Symmetry code: (A) x, 1 − y, −0.5 + z.]
	Fig. 2. The larger 28-membered ring and smaller eight-membered ring in (I). The o-phenanthroline molecule has been omitted for clarity. [Symmetry codes: (A) x, 1 − y, −0.5 + z; (B) x, 1 − y, 0.5 + z; (C) 1 − x, 1 − y, 1 − z; (D) 1 − x, y, 1.5 − z; (E) 1 − x, 1 − y, 2 − z.]
	Fig. 3. A two-dimensional sheet in complex (I), viewed along b.

di-µ-fumatato-bis(o-phenanthroline)dicobalt(II)

Crystal data

[Co2(C4H2O4)2(C12H8N2)2]	F(000) = 1432
Mr = 706.38	Dx = 1.683 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 24016 reflections
a = 12.264 (3) Å	θ = 1.7–27.5°
b = 10.111 (2) Å	µ = 1.25 mm^−1
c = 22.650 (5) Å	T = 293 K
β = 96.89 (3)°	Block, purple
V = 2788.2 (11) Å^3	0.44 × 0.37 × 0.24 mm
Z = 4

Data collection

Rigaku RAXIS-RAPID diffractometer	6376 independent reflections
Radiation source: rotor-target	5500 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 1.7°
ω scan	h = 0→15
Absorption correction: multi-scan Higashi (1995)	k = 0→13
Tmin = 0.549, Tmax = 0.744	l = −29→29
24016 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0564P)^2] where P = (Fo^2 + 2Fc^2)/3
6376 reflections	(Δ/σ)max = 0.003
415 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.58 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	0.78426 (13)	0.43497 (16)	0.67346 (7)	0.0149 (3)
C2	0.76938 (14)	0.53392 (16)	0.72081 (7)	0.0185 (3)
H2	0.8104	0.6115	0.7222	0.022*
C3	0.70058 (14)	0.51650 (16)	0.76093 (7)	0.0178 (3)
H3	0.6581	0.4401	0.7592	0.021*
C4	0.68880 (13)	0.61492 (16)	0.80881 (7)	0.0141 (3)
C5	0.88864 (13)	0.63208 (16)	0.97498 (7)	0.0135 (3)
C6	0.97230 (13)	0.52378 (16)	0.97524 (7)	0.0146 (3)
H6	0.9861	0.4882	0.9390	0.018*
C7	0.60453 (13)	0.64443 (16)	1.00341 (7)	0.0145 (3)
C8	0.51762 (13)	0.54595 (17)	0.98244 (7)	0.0167 (3)
H8	0.4867	0.5491	0.9429	0.020*
C101	0.66938 (14)	0.01467 (17)	0.55520 (7)	0.0163 (3)
H101	0.6142	0.0685	0.5365	0.020*
C102	0.65370 (15)	−0.12319 (18)	0.55331 (7)	0.0200 (4)
H102	0.5886	−0.1588	0.5347	0.024*
C103	0.73530 (15)	−0.20485 (17)	0.57919 (8)	0.0201 (4)
H103	0.7269	−0.2962	0.5774	0.024*
C104	0.83213 (14)	−0.14824 (17)	0.60860 (7)	0.0168 (3)
C105	0.83947 (13)	−0.00902 (16)	0.60964 (7)	0.0128 (3)
C106	0.92195 (16)	−0.22544 (17)	0.63677 (9)	0.0212 (4)
H106	0.9187	−0.3172	0.6344	0.025*
C107	1.01089 (15)	−0.16713 (18)	0.66659 (8)	0.0217 (4)
H107	1.0675	−0.2193	0.6850	0.026*
C108	1.01956 (14)	−0.02520 (17)	0.67040 (7)	0.0167 (3)
C109	0.93503 (13)	0.05296 (16)	0.64097 (7)	0.0135 (3)
C110	1.10878 (14)	0.04141 (19)	0.70208 (8)	0.0214 (4)
H110	1.1663	−0.0065	0.7223	0.026*
C111	1.11090 (14)	0.17744 (19)	0.70315 (7)	0.0206 (4)
H111	1.1688	0.2225	0.7246	0.025*
C112	1.02364 (14)	0.24713 (17)	0.67100 (8)	0.0174 (3)
H112	1.0260	0.3391	0.6711	0.021*
C201	0.46772 (14)	0.83281 (17)	0.82226 (7)	0.0162 (3)
H201	0.4575	0.7422	0.8172	0.019*
C202	0.38576 (14)	0.91871 (19)	0.79549 (7)	0.0201 (4)
H202	0.3235	0.8853	0.7729	0.024*
C203	0.39937 (14)	1.05284 (18)	0.80336 (7)	0.0196 (4)
H203	0.3458	1.1112	0.7866	0.024*
C204	0.49575 (14)	1.10142 (17)	0.83724 (7)	0.0163 (3)
C205	0.57327 (13)	1.00775 (15)	0.86112 (7)	0.0127 (3)
C206	0.51798 (16)	1.23929 (17)	0.84749 (8)	0.0221 (4)
H206	0.4664	1.3017	0.8323	0.026*
C207	0.61298 (16)	1.27995 (17)	0.87891 (8)	0.0226 (4)
H207	0.6253	1.3699	0.8851	0.027*
C208	0.69516 (14)	1.18649 (17)	0.90284 (7)	0.0169 (3)
C209	0.67479 (13)	1.05033 (16)	0.89431 (7)	0.0127 (3)
C210	0.79664 (16)	1.22348 (18)	0.93420 (8)	0.0217 (4)
H210	0.8138	1.3124	0.9405	0.026*
C211	0.87007 (14)	1.12743 (18)	0.95542 (7)	0.0208 (4)
H211	0.9376	1.1506	0.9760	0.025*
C212	0.84218 (14)	0.99361 (18)	0.94577 (7)	0.0172 (3)
H212	0.8920	0.9293	0.9610	0.021*
N1	0.93849 (11)	0.18762 (13)	0.64073 (6)	0.0134 (3)
N2	0.75940 (11)	0.07160 (13)	0.58248 (6)	0.0131 (3)
N3	0.55857 (11)	0.87480 (13)	0.85426 (6)	0.0131 (3)
N4	0.74773 (11)	0.95512 (13)	0.91587 (6)	0.0128 (3)
O1	0.84044 (10)	0.46731 (12)	0.63247 (5)	0.0192 (3)
O2	0.74096 (10)	0.32169 (11)	0.67522 (5)	0.0157 (2)
O3	0.73935 (10)	0.72436 (11)	0.80923 (5)	0.0155 (2)
O4	0.63002 (10)	0.58483 (12)	0.84911 (5)	0.0182 (3)
O5	0.82484 (10)	0.64344 (13)	0.92737 (5)	0.0225 (3)
O6	0.88844 (10)	0.70520 (12)	1.02024 (5)	0.0152 (2)
O7	0.61330 (10)	0.74478 (11)	0.97060 (5)	0.0157 (2)
O8	0.66130 (10)	0.62482 (13)	1.05234 (5)	0.0221 (3)
Co1	0.798748 (17)	0.27685 (2)	0.590143 (9)	0.01125 (7)
Co2	0.691125 (18)	0.76042 (2)	0.897057 (9)	0.01112 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0159 (8)	0.0154 (7)	0.0129 (7)	0.0024 (6)	−0.0002 (6)	−0.0024 (6)
C2	0.0243 (9)	0.0137 (8)	0.0178 (8)	−0.0014 (6)	0.0033 (7)	−0.0036 (6)
C3	0.0224 (9)	0.0135 (8)	0.0174 (8)	−0.0006 (6)	0.0022 (7)	−0.0044 (6)
C4	0.0154 (8)	0.0144 (7)	0.0120 (7)	0.0042 (6)	−0.0005 (6)	−0.0009 (6)
C5	0.0129 (7)	0.0127 (7)	0.0147 (7)	0.0007 (6)	0.0013 (6)	0.0023 (6)
C6	0.0157 (8)	0.0145 (7)	0.0137 (7)	0.0026 (6)	0.0019 (6)	−0.0015 (6)
C7	0.0146 (8)	0.0159 (8)	0.0133 (7)	−0.0021 (6)	0.0023 (6)	−0.0009 (6)
C8	0.0179 (8)	0.0184 (8)	0.0130 (7)	−0.0039 (7)	−0.0014 (6)	−0.0004 (6)
C101	0.0161 (8)	0.0190 (8)	0.0140 (7)	−0.0037 (6)	0.0021 (6)	−0.0007 (6)
C102	0.0216 (9)	0.0206 (9)	0.0178 (8)	−0.0083 (7)	0.0025 (7)	−0.0025 (7)
C103	0.0263 (10)	0.0134 (8)	0.0217 (8)	−0.0045 (7)	0.0073 (7)	−0.0020 (7)
C104	0.0204 (8)	0.0138 (8)	0.0170 (8)	−0.0007 (6)	0.0060 (7)	0.0012 (6)
C105	0.0143 (8)	0.0132 (8)	0.0117 (7)	0.0014 (6)	0.0044 (6)	0.0009 (6)
C106	0.0257 (10)	0.0129 (8)	0.0267 (9)	0.0046 (7)	0.0103 (8)	0.0040 (7)
C107	0.0208 (9)	0.0195 (9)	0.0255 (9)	0.0088 (7)	0.0053 (7)	0.0084 (7)
C108	0.0153 (8)	0.0203 (8)	0.0152 (8)	0.0050 (6)	0.0045 (6)	0.0041 (6)
C109	0.0143 (8)	0.0154 (7)	0.0113 (7)	0.0009 (6)	0.0038 (6)	0.0010 (6)
C110	0.0158 (8)	0.0289 (10)	0.0191 (8)	0.0055 (7)	0.0008 (7)	0.0044 (7)
C111	0.0141 (8)	0.0296 (10)	0.0170 (8)	−0.0019 (7)	−0.0028 (6)	−0.0002 (7)
C112	0.0163 (8)	0.0187 (8)	0.0169 (8)	0.0002 (6)	0.0011 (7)	−0.0019 (6)
C201	0.0164 (8)	0.0169 (8)	0.0152 (7)	0.0016 (6)	0.0009 (6)	−0.0025 (6)
C202	0.0165 (8)	0.0265 (9)	0.0166 (8)	0.0022 (7)	−0.0014 (7)	−0.0024 (7)
C203	0.0165 (8)	0.0256 (9)	0.0163 (8)	0.0085 (7)	−0.0002 (6)	0.0021 (7)
C204	0.0180 (8)	0.0160 (8)	0.0153 (7)	0.0039 (6)	0.0038 (6)	0.0026 (6)
C205	0.0148 (8)	0.0122 (7)	0.0116 (7)	0.0016 (6)	0.0044 (6)	0.0009 (6)
C206	0.0267 (10)	0.0141 (8)	0.0259 (10)	0.0076 (7)	0.0052 (8)	0.0048 (7)
C207	0.0307 (11)	0.0102 (8)	0.0279 (9)	0.0021 (7)	0.0081 (8)	0.0012 (7)
C208	0.0200 (9)	0.0135 (8)	0.0181 (8)	−0.0018 (6)	0.0053 (7)	−0.0003 (6)
C209	0.0149 (8)	0.0117 (7)	0.0122 (7)	0.0003 (6)	0.0047 (6)	0.0008 (6)
C210	0.0263 (10)	0.0160 (8)	0.0236 (9)	−0.0086 (7)	0.0071 (8)	−0.0042 (7)
C211	0.0180 (8)	0.0259 (9)	0.0184 (8)	−0.0090 (7)	0.0019 (7)	−0.0035 (7)
C212	0.0153 (8)	0.0216 (8)	0.0146 (7)	−0.0014 (6)	0.0008 (6)	0.0000 (6)
N1	0.0143 (7)	0.0150 (7)	0.0110 (6)	0.0007 (5)	0.0013 (5)	−0.0002 (5)
N2	0.0144 (7)	0.0140 (6)	0.0110 (6)	0.0018 (5)	0.0019 (5)	0.0006 (5)
N3	0.0146 (7)	0.0132 (6)	0.0117 (6)	0.0008 (5)	0.0018 (5)	−0.0007 (5)
N4	0.0129 (6)	0.0139 (6)	0.0120 (6)	−0.0003 (5)	0.0024 (5)	0.0004 (5)
O1	0.0263 (7)	0.0152 (6)	0.0172 (6)	−0.0031 (5)	0.0074 (5)	−0.0032 (5)
O2	0.0188 (6)	0.0126 (5)	0.0159 (6)	−0.0005 (4)	0.0027 (5)	−0.0026 (4)
O3	0.0189 (6)	0.0136 (6)	0.0138 (5)	−0.0006 (4)	0.0015 (5)	−0.0015 (4)
O4	0.0249 (6)	0.0138 (6)	0.0167 (6)	−0.0002 (5)	0.0065 (5)	−0.0016 (5)
O5	0.0254 (7)	0.0246 (7)	0.0154 (6)	0.0135 (5)	−0.0060 (5)	−0.0024 (5)
O6	0.0170 (6)	0.0151 (5)	0.0138 (5)	0.0011 (4)	0.0026 (4)	−0.0016 (4)
O7	0.0197 (6)	0.0135 (5)	0.0145 (5)	−0.0011 (4)	0.0043 (5)	0.0010 (4)
O8	0.0228 (6)	0.0244 (7)	0.0170 (6)	−0.0122 (5)	−0.0068 (5)	0.0052 (5)
Co1	0.01303 (12)	0.01011 (12)	0.01023 (11)	0.00141 (7)	−0.00012 (8)	−0.00075 (7)
Co2	0.01319 (12)	0.00988 (12)	0.00997 (11)	0.00183 (7)	0.00015 (8)	0.00022 (7)

Geometric parameters (Å, º)

C1—O1	1.264 (2)	C112—N1	1.323 (2)
C1—O2	1.265 (2)	C112—H112	0.9300
C1—C2	1.494 (2)	C201—N3	1.324 (2)
C2—C3	1.324 (3)	C201—C202	1.409 (2)
C2—H2	0.9300	C201—H201	0.9300
C3—C4	1.491 (2)	C202—C203	1.375 (3)
C3—H3	0.9300	C202—H202	0.9300
C4—O4	1.266 (2)	C203—C204	1.418 (2)
C4—O3	1.268 (2)	C203—H203	0.9300
C5—O5	1.2593 (19)	C204—C205	1.404 (2)
C5—O6	1.2641 (19)	C204—C206	1.434 (2)
C5—C6	1.500 (2)	C205—N3	1.363 (2)
C6—C6^i	1.330 (3)	C205—C209	1.441 (2)
C6—H6	0.9300	C206—C207	1.354 (3)
C7—O8	1.2519 (19)	C206—H206	0.9300
C7—O7	1.270 (2)	C207—C208	1.439 (2)
C7—C8	1.494 (2)	C207—H207	0.9300
C8—C8^ii	1.329 (3)	C208—C210	1.408 (2)
C8—H8	0.9300	C208—C209	1.408 (2)
C101—N2	1.330 (2)	C209—N4	1.364 (2)
C101—C102	1.407 (2)	C210—C211	1.372 (3)
C101—H101	0.9300	C210—H210	0.9300
C102—C103	1.373 (3)	C211—C212	1.406 (3)
C102—H102	0.9300	C211—H211	0.9300
C103—C104	1.411 (2)	C212—N4	1.328 (2)
C103—H103	0.9300	C212—H212	0.9300
C104—C105	1.410 (2)	N1—Co1	2.1432 (15)
C104—C106	1.436 (2)	N2—Co1	2.1329 (14)
C105—N2	1.365 (2)	N3—Co2	2.1312 (14)
C105—C109	1.439 (2)	N4—Co2	2.1136 (14)
C106—C107	1.348 (3)	O1—Co1	2.1843 (12)
C106—H106	0.9300	O2—Co1	2.1792 (12)
C107—C108	1.441 (2)	O3—Co2	2.1731 (13)
C107—H107	0.9300	O4—Co2	2.1674 (12)
C108—C110	1.406 (3)	O5—Co2	2.0712 (12)
C108—C109	1.406 (2)	O6—Co1^iii	2.0415 (13)
C109—N1	1.362 (2)	O7—Co2	2.0228 (13)
C110—C111	1.376 (3)	O8—Co1^iii	2.0535 (12)
C110—H110	0.9300	Co1—O6^iv	2.0415 (13)
C111—C112	1.409 (2)	Co1—O8^iv	2.0535 (12)
C111—H111	0.9300
O1—C1—O2	121.70 (15)	N3—C205—C209	116.65 (14)
O1—C1—C2	118.59 (15)	C204—C205—C209	120.16 (15)
O2—C1—C2	119.71 (15)	C207—C206—C204	121.00 (16)
C3—C2—C1	123.13 (16)	C207—C206—H206	119.5
C3—C2—H2	118.4	C204—C206—H206	119.5
C1—C2—H2	118.4	C206—C207—C208	121.20 (16)
C2—C3—C4	122.38 (16)	C206—C207—H207	119.4
C2—C3—H3	118.8	C208—C207—H207	119.4
C4—C3—H3	118.8	C210—C208—C209	117.42 (16)
O4—C4—O3	121.63 (14)	C210—C208—C207	123.53 (17)
O4—C4—C3	118.49 (15)	C209—C208—C207	119.04 (16)
O3—C4—C3	119.86 (15)	N4—C209—C208	122.88 (15)
O5—C5—O6	125.42 (15)	N4—C209—C205	117.67 (15)
O5—C5—C6	115.11 (14)	C208—C209—C205	119.45 (15)
O6—C5—C6	119.44 (14)	C211—C210—C208	119.50 (16)
C6^i—C6—C5	123.19 (19)	C211—C210—H210	120.3
C6^i—C6—H6	118.4	C208—C210—H210	120.3
C5—C6—H6	118.4	C210—C211—C212	119.31 (16)
O8—C7—O7	124.58 (15)	C210—C211—H211	120.3
O8—C7—C8	118.40 (15)	C212—C211—H211	120.3
O7—C7—C8	116.99 (14)	N4—C212—C211	122.84 (16)
C8^ii—C8—C7	123.15 (19)	N4—C212—H212	118.6
C8^ii—C8—H8	118.4	C211—C212—H212	118.6
C7—C8—H8	118.4	C112—N1—C109	118.39 (15)
N2—C101—C102	123.08 (16)	C112—N1—Co1	128.06 (12)
N2—C101—H101	118.5	C109—N1—Co1	113.55 (11)
C102—C101—H101	118.5	C101—N2—C105	117.61 (15)
C103—C102—C101	119.51 (16)	C101—N2—Co1	128.76 (11)
C103—C102—H102	120.2	C105—N2—Co1	113.64 (11)
C101—C102—H102	120.2	C201—N3—C205	118.03 (14)
C102—C103—C104	119.11 (16)	C201—N3—Co2	128.38 (12)
C102—C103—H103	120.4	C205—N3—Co2	113.58 (11)
C104—C103—H103	120.4	C212—N4—C209	118.05 (15)
C105—C104—C103	117.46 (16)	C212—N4—Co2	128.39 (12)
C105—C104—C106	119.41 (16)	C209—N4—Co2	113.56 (11)
C103—C104—C106	123.13 (16)	C1—O1—Co1	88.55 (9)
N2—C105—C104	123.19 (16)	C1—O2—Co1	88.75 (10)
N2—C105—C109	117.50 (15)	C4—O3—Co2	88.10 (9)
C104—C105—C109	119.31 (15)	C4—O4—Co2	88.39 (10)
C107—C106—C104	121.10 (16)	C5—O5—Co2	136.21 (11)
C107—C106—H106	119.4	C5—O6—Co1^iii	137.27 (11)
C104—C106—H106	119.4	C7—O7—Co2	128.74 (11)
C106—C107—C108	121.01 (16)	C7—O8—Co1^iii	129.35 (11)
C106—C107—H107	119.5	O6^iv—Co1—O8^iv	97.19 (5)
C108—C107—H107	119.5	O6^iv—Co1—N2	99.27 (5)
C110—C108—C109	117.20 (16)	O8^iv—Co1—N2	105.71 (5)
C110—C108—C107	123.70 (16)	O6^iv—Co1—N1	88.94 (5)
C109—C108—C107	119.10 (16)	O8^iv—Co1—N1	172.12 (5)
N1—C109—C108	122.81 (16)	N2—Co1—N1	78.03 (5)
N1—C109—C105	117.22 (15)	O6^iv—Co1—O2	158.43 (5)
C108—C109—C105	119.97 (15)	O8^iv—Co1—O2	86.00 (5)
C111—C110—C108	119.97 (16)	N2—Co1—O2	100.37 (5)
C111—C110—H110	120.0	N1—Co1—O2	86.49 (5)
C108—C110—H110	120.0	O6^iv—Co1—O1	98.19 (5)
C110—C111—C112	118.64 (16)	O8^iv—Co1—O1	83.88 (5)
C110—C111—H111	120.7	N2—Co1—O1	158.78 (5)
C112—C111—H111	120.7	N1—Co1—O1	90.36 (5)
N1—C112—C111	122.94 (16)	O2—Co1—O1	60.81 (4)
N1—C112—H112	118.5	O7—Co2—O5	96.62 (5)
C111—C112—H112	118.5	O7—Co2—N4	94.75 (5)
N3—C201—C202	123.22 (16)	O5—Co2—N4	103.72 (5)
N3—C201—H201	118.4	O7—Co2—N3	90.43 (5)
C202—C201—H201	118.4	O5—Co2—N3	172.37 (5)
C203—C202—C201	118.86 (16)	N4—Co2—N3	78.49 (5)
C203—C202—H202	120.6	O7—Co2—O4	100.35 (5)
C201—C202—H202	120.6	O5—Co2—O4	84.88 (5)
C202—C203—C204	119.48 (16)	N4—Co2—O4	161.68 (5)
C202—C203—H203	120.3	N3—Co2—O4	91.00 (5)
C204—C203—H203	120.3	O7—Co2—O3	161.40 (5)
C205—C204—C203	117.20 (16)	O5—Co2—O3	85.19 (5)
C205—C204—C206	119.12 (16)	N4—Co2—O3	102.82 (5)
C203—C204—C206	123.67 (16)	N3—Co2—O3	87.20 (5)
N3—C205—C204	123.19 (15)	O4—Co2—O3	61.29 (4)
O1—C1—C2—C3	170.72 (16)	C8—C7—O7—Co2	−81.35 (18)
O2—C1—C2—C3	−9.4 (3)	O7—C7—O8—Co1^iii	−10.8 (3)
C1—C2—C3—C4	178.48 (14)	C8—C7—O8—Co1^iii	171.29 (11)
C2—C3—C4—O4	−172.67 (16)	C101—N2—Co1—O6^iv	−95.35 (14)
C2—C3—C4—O3	5.6 (2)	C105—N2—Co1—O6^iv	84.46 (11)
O5—C5—C6—C6^i	−163.1 (2)	C101—N2—Co1—O8^iv	4.89 (15)
O6—C5—C6—C6^i	18.5 (3)	C105—N2—Co1—O8^iv	−175.31 (10)
O8—C7—C8—C8^ii	14.0 (3)	C101—N2—Co1—N1	177.74 (15)
O7—C7—C8—C8^ii	−164.1 (2)	C105—N2—Co1—N1	−2.45 (10)
N2—C101—C102—C103	−1.8 (3)	C101—N2—Co1—O2	93.62 (14)
C101—C102—C103—C104	1.7 (3)	C105—N2—Co1—O2	−86.57 (11)
C102—C103—C104—C105	0.0 (2)	C101—N2—Co1—O1	119.64 (16)
C102—C103—C104—C106	−179.79 (17)	C105—N2—Co1—O1	−60.56 (19)
C103—C104—C105—N2	−1.8 (2)	C101—N2—Co1—C1	98.92 (15)
C106—C104—C105—N2	177.98 (15)	C105—N2—Co1—C1	−81.27 (12)
C103—C104—C105—C109	177.77 (14)	C112—N1—Co1—O6^iv	83.28 (15)
C106—C104—C105—C109	−2.5 (2)	C109—N1—Co1—O6^iv	−97.48 (11)
C105—C104—C106—C107	3.2 (3)	C112—N1—Co1—N2	−177.02 (15)
C103—C104—C106—C107	−177.08 (17)	C109—N1—Co1—N2	2.23 (11)
C104—C106—C107—C108	−1.0 (3)	C112—N1—Co1—O2	−75.63 (14)
C106—C107—C108—C110	178.29 (17)	C109—N1—Co1—O2	103.61 (11)
C106—C107—C108—C109	−1.9 (3)	C112—N1—Co1—O1	−14.91 (15)
C110—C108—C109—N1	2.0 (2)	C109—N1—Co1—O1	164.33 (11)
C107—C108—C109—N1	−177.83 (16)	C112—N1—Co1—C1	−45.31 (15)
C110—C108—C109—C105	−177.64 (15)	C109—N1—Co1—C1	133.94 (12)
C107—C108—C109—C105	2.5 (2)	C1—O2—Co1—O6^iv	16.76 (17)
N2—C105—C109—N1	−0.4 (2)	C1—O2—Co1—O8^iv	−82.72 (10)
C104—C105—C109—N1	179.97 (15)	C1—O2—Co1—N2	172.02 (9)
N2—C105—C109—C108	179.24 (14)	C1—O2—Co1—N1	94.88 (10)
C104—C105—C109—C108	−0.3 (2)	C1—O2—Co1—O1	2.50 (9)
C109—C108—C110—C111	−0.2 (3)	C1—O1—Co1—O6^iv	−177.25 (9)
C107—C108—C110—C111	179.61 (17)	C1—O1—Co1—O8^iv	86.33 (10)
C108—C110—C111—C112	−1.4 (3)	C1—O1—Co1—N2	−32.12 (19)
C110—C111—C112—N1	1.4 (3)	C1—O1—Co1—N1	−88.28 (10)
N3—C201—C202—C203	−0.9 (3)	C1—O1—Co1—O2	−2.50 (9)
C201—C202—C203—C204	1.0 (3)	O1—C1—Co1—O6^iv	3.48 (12)
C202—C203—C204—C205	0.1 (2)	O2—C1—Co1—O6^iv	−172.21 (8)
C202—C203—C204—C206	179.38 (17)	O1—C1—Co1—O8^iv	−90.06 (10)
C203—C204—C205—N3	−1.5 (2)	O2—C1—Co1—O8^iv	94.26 (9)
C206—C204—C205—N3	179.21 (16)	O1—C1—Co1—N2	165.35 (9)
C203—C204—C205—C209	177.89 (14)	O2—C1—Co1—N2	−10.33 (12)
C206—C204—C205—C209	−1.4 (2)	O1—C1—Co1—N1	91.67 (10)
C205—C204—C206—C207	1.0 (3)	O2—C1—Co1—N1	−84.02 (9)
C203—C204—C206—C207	−178.19 (17)	O1—C1—Co1—O2	175.69 (15)
C204—C206—C207—C208	0.3 (3)	O2—C1—Co1—O1	−175.69 (15)
C206—C207—C208—C210	177.95 (17)	C7—O7—Co2—O5	−38.86 (14)
C206—C207—C208—C209	−1.4 (3)	C7—O7—Co2—N4	−143.29 (14)
C210—C208—C209—N4	1.2 (2)	C7—O7—Co2—N3	138.22 (14)
C207—C208—C209—N4	−179.46 (15)	C7—O7—Co2—O4	47.12 (14)
C210—C208—C209—C205	−178.37 (14)	C7—O7—Co2—O3	55.7 (2)
C207—C208—C209—C205	1.0 (2)	C7—O7—Co2—C4	46.26 (16)
N3—C205—C209—N4	0.2 (2)	C5—O5—Co2—O7	−44.59 (18)
C204—C205—C209—N4	−179.19 (14)	C5—O5—Co2—N4	51.96 (18)
N3—C205—C209—C208	179.81 (14)	C5—O5—Co2—O4	−144.45 (18)
C204—C205—C209—C208	0.4 (2)	C5—O5—Co2—O3	154.01 (18)
C209—C208—C210—C211	−0.7 (3)	C5—O5—Co2—C4	−175.22 (18)
C207—C208—C210—C211	−179.99 (17)	C212—N4—Co2—O7	91.49 (14)
C208—C210—C211—C212	−0.4 (3)	C209—N4—Co2—O7	−87.68 (11)
C210—C211—C212—N4	1.2 (3)	C212—N4—Co2—O5	−6.52 (15)
C111—C112—N1—C109	0.3 (3)	C209—N4—Co2—O5	174.31 (10)
C111—C112—N1—Co1	179.53 (12)	C212—N4—Co2—N3	−179.04 (15)
C108—C109—N1—C112	−2.1 (2)	C209—N4—Co2—N3	1.80 (10)
C105—C109—N1—C112	177.61 (15)	C212—N4—Co2—O4	−122.96 (17)
C108—C109—N1—Co1	178.61 (12)	C209—N4—Co2—O4	57.9 (2)
C105—C109—N1—Co1	−1.72 (18)	C212—N4—Co2—O3	−94.63 (14)
C102—C101—N2—C105	0.0 (2)	C209—N4—Co2—O3	86.20 (11)
C102—C101—N2—Co1	179.84 (12)	C212—N4—Co2—C4	−98.43 (15)
C104—C105—N2—C101	1.8 (2)	C209—N4—Co2—C4	82.40 (12)
C109—C105—N2—C101	−177.79 (14)	C201—N3—Co2—O7	−87.94 (14)
C104—C105—N2—Co1	−178.05 (13)	C205—N3—Co2—O7	93.08 (11)
C109—C105—N2—Co1	2.38 (17)	C201—N3—Co2—N4	177.30 (15)
C202—C201—N3—C205	−0.4 (2)	C205—N3—Co2—N4	−1.68 (11)
C202—C201—N3—Co2	−179.37 (12)	C201—N3—Co2—O4	12.42 (14)
C204—C205—N3—C201	1.7 (2)	C205—N3—Co2—O4	−166.56 (11)
C209—C205—N3—C201	−177.76 (14)	C201—N3—Co2—O3	73.61 (14)
C204—C205—N3—Co2	−179.25 (12)	C205—N3—Co2—O3	−105.37 (11)
C209—C205—N3—Co2	1.33 (17)	C201—N3—Co2—C4	43.12 (14)
C211—C212—N4—C209	−0.7 (2)	C205—N3—Co2—C4	−135.86 (11)
C211—C212—N4—Co2	−179.81 (12)	C4—O4—Co2—O7	−178.73 (9)
C208—C209—N4—C212	−0.5 (2)	C4—O4—Co2—O5	−82.91 (10)
C205—C209—N4—C212	179.04 (14)	C4—O4—Co2—N4	36.2 (2)
C208—C209—N4—Co2	178.75 (12)	C4—O4—Co2—N3	90.65 (9)
C205—C209—N4—Co2	−1.70 (17)	C4—O4—Co2—O3	4.40 (8)
O2—C1—O1—Co1	4.43 (15)	C4—O3—Co2—O7	−14.07 (19)
C2—C1—O1—Co1	−175.67 (13)	C4—O3—Co2—O5	82.40 (9)
O1—C1—O2—Co1	−4.44 (15)	C4—O3—Co2—N4	−174.60 (9)
C2—C1—O2—Co1	175.66 (13)	C4—O3—Co2—N3	−97.07 (9)
O4—C4—O3—Co2	7.76 (15)	C4—O3—Co2—O4	−4.39 (8)
C3—C4—O3—Co2	−170.44 (13)	O4—C4—Co2—O7	1.66 (12)
O3—C4—O4—Co2	−7.78 (15)	O4—C4—Co2—O5	93.48 (10)
C3—C4—O4—Co2	170.44 (13)	O3—C4—Co2—O5	−94.07 (9)
O6—C5—O5—Co2	−4.6 (3)	O4—C4—Co2—N4	−165.19 (9)
C6—C5—O5—Co2	177.10 (12)	O3—C4—Co2—N4	7.26 (12)
O5—C5—O6—Co1^iii	78.8 (2)	O4—C4—Co2—N3	−89.95 (9)
C6—C5—O6—Co1^iii	−102.97 (18)	O3—C4—Co2—N3	82.49 (9)
O8—C7—O7—Co2	100.68 (18)	O4—C4—Co2—O3	−172.44 (14)

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