Crystal structure of a heterometallic coordination polymer: catena-poly[[[tetra-aqua-cobalt(II)]-μ-pyridine-2,6-di-carboxyl-ato-calcium(II)-μ-pyridine-2,6-di-carboxyl-ato] dihydrate].

In the crystal of the title polymeric complex, {[CoCa(C7H3NO4)2(H2O)4]·2H2O} n (1), the CoII ion is N,O,O'-chelated by two pyridine-2,6-di-carboxyl-ate anions in a distorted N2O4 octa-hedral geometry, and two carboxyl-ate O atoms of pyridine-2,6-di-carboxyl-ate anions bridge tetra-aqua-calcium(II) units to form polymeric chains propagating along the b-axis direction. In the crystal, O-H⋯O and C-H⋯O hydrogen bonds, and offset π-π stacking inter-actions [inter-centroid distances = 3.551 (1) and 3.746 (1) Å] involving inversion-related pyridine rings link the polymeric chains and lattice water mol-ecules to form a supra-molecular three-dimensional framework.

Chemical context

The controllable synthesis of heterometallic n class="Chemical">polymers, with their fascinating structures and outstanding properties, is still a challenge in crystal engineering (Cai et al., 2012 ▸; Ma et al., 2014 ▸; Sun et al., 2014 ▸; Ward, 2007 ▸). The influencing factors include the coordination geometry of the metal centre, reaction of solvent, temperature, metal-to-ligand ratio, pH value, the nature of ligand, and so on (Chen et al., 2012 ▸; Guo & Cao, 2009 ▸; Ni et al., 2009 ▸; Yamada et al., 2011 ▸). According to our earlier study (Sun et al., 2016 ▸), heterometallic complexes containing both alkaline earth metals and d-block transition metals are available because the former are structurally malleable and they have a strong affinity to O atoms rather than N atoms (Cao et al., 2015 ▸; Yu et al., 2013 ▸), and the latter have a strong tendency to coordinate to both N- and O-atom donors (Hu et al., 2013 ▸; Zhang et al., 2013 ▸). Meanwhile, pyridinedi­carb­oxy­lic acid (H2pdc) is widely used in the construction of various metal–organic frameworks for two main reasons. Firstly, the O and N atoms in these ligands made them easy to chelate or bridge metal ions. Secondly, they can be completely or partially deprotonated to generate Hpdc− or pyc2−, displaying a variety of coordination modes. As a part of our ongoing studies on heterometallic frameworks, we describe here the synthesis and crystal structure of the title complex,1

Structural commentary

The asymmetric unit of 1 contains one cobalt centre, one n class="Chemical">calcium centre, two pdc2− anions, four coordinated water mol­ecules and two lattice water mol­ecules (Fig. 1 ▸). The Co—O(N) bond lengths are in the range 2.0172 (13)–2.2018 (12) Å and the Ca—O bond lengths are in the range 2.3358 (12)–2.3727 (12) Å (Table 1 ▸). All the data are comparable to those reported for other related CoII–pdc and CaII–pdc complexes (Jung et al., 2008 ▸; Shi et al., 2012 ▸). Each CoII centre is chelated by four O and two N atoms from two pdc2− anions, forming a distorted octa­hedral geometry. The mean deviation of the equatorial plane constructed by atoms N1, N2, O5 and O7 is 0.02 Å. Each CaII centre is six-coordinated by two carboxyl­ate O atoms from two pdc2− anions and four water mol­ecules, displaying a distorted octa­hedron (Fig. 1 ▸). The mean deviation of the equatorial plane constructed by atoms O4, OW1, OW3 and OW4 is 0.08 Å. The CoN2O4 and CaO6 polyhedra are linked by pdc2− anions to form polymeric chains along the b-axis direction (Fig. 2 ▸).

Figure 1

The coordination mode and atom-numbering scheme for the asymmetric unit of 1. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (A) x, y − 1, z; (B) x, y + 1, z].

Table 1

Selected bond lengths (Å)

Co1—N1	2.0172 (13)	Ca1—O4i	2.3358 (12)
Co1—N2	2.0199 (13)	Ca1—OW4	2.3449 (13)
Co1—O5	2.1466 (12)	Ca1—O8	2.3458 (12)
Co1—O3	2.1469 (13)	Ca1—OW1	2.3476 (13)
Co1—O1	2.1643 (12)	Ca1—OW3	2.3719 (13)
Co1—O7	2.2018 (12)	Ca1—OW2	2.3727 (12)

Symmetry code: (i) .

Figure 2

The chain formed by pdc2− anions, and CoII and CaII centres, propagating along the b-axis direction.

Supra­molcular features

In the crystal of 1, the polymeric chains are linked by O—H⋯O and C—H⋯O n class="Chemical">hydrogen bonds involving the water mol­ecules and carboxyl groups, so forming a supra­molecular three-dimensional framework (Table 2 ▸ and Fig. 3 ▸). Within the framework, inversion-related pyridine rings are linked by offset π–π inter­actions reinforcing the framework: Cg5⋯Cg5vii = 3.746 (1) Å, inter­planar distance = 3.309 (1) Å, slippage = 1.755 Å; Cg6⋯Cg6viii = 3.551 (1) Å, inter­planar distance = 3.279 (1) Å, slippage = 1.363 Å; Cg5 and Cg6 are the centroids of pyridine rings N1/C1–C5 and N2/C8–C12, respectively; symmetry codes: (vii) −x + 1, −y + 1, −z; (viii) −x + 1, −y, −z + 1.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—HW1A⋯O2ii	0.84 (1)	1.93 (1)	2.769 (2)	171 (3)
OW1—HW1B⋯O2iii	0.85 (1)	2.06 (1)	2.870 (2)	161 (3)
OW2—HW2A⋯OW6	0.85 (1)	2.00 (1)	2.846 (2)	175 (3)
OW2—HW2B⋯O5iv	0.85 (1)	1.89 (1)	2.730 (2)	173 (3)
OW3—HW3A⋯O1ii	0.84 (1)	1.99 (1)	2.817 (2)	172 (3)
OW3—HW3B⋯O6v	0.84 (1)	2.12 (1)	2.923 (2)	162 (3)
OW4—HW4A⋯O6iv	0.84 (1)	2.02 (1)	2.851 (2)	172 (3)
OW4—HW4B⋯OW5	0.84 (1)	1.90 (1)	2.741 (2)	173 (3)
OW5—HW5A⋯O8vi	0.85 (1)	2.10 (1)	2.946 (2)	174 (3)
OW5—HW5B⋯O3v	0.85 (1)	2.08 (2)	2.870 (2)	153 (3)
OW6—HW6A⋯O7i	0.84 (1)	2.13 (1)	2.945 (2)	163 (3)
OW6—HW6B⋯O2iv	0.84 (1)	2.34 (1)	3.140 (2)	160 (3)
C2—H2A⋯O7iii	0.93	2.56	3.448 (2)	160
C10—H10A⋯O3v	0.93	2.55	3.246 (2)	132

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 3

A view along the c axis of the crystal packing of 1. The hydrogen bonds are shown as dashed lines (see Table 2 ▸). For clarity, only the H atoms involved in these inter­actions have been included.

Database survey

A search of the Cambridge Structural Database (Version 5.39, last update February 2018; Groom et al., 2016 ▸) for cobalt complexes of the ligand n class="Chemical">pyridine-2,6-di­carb­oxy­lic acid gave 180 hits, of which 58 are polymeric complexes. They include a number of alkali metal heterometallic coordination polymes, four involving K+ and seven Na+, but no alkali earth metal heterometallic coordination polymers. Hence, the title compound 1 is the first reported heterometallic coordination polymer involving the ligand pyridine-2,6-di­carb­oxy­lic acid, CoII and an alkali earth metal (CaII).

Synthesis and crystallization

A mixture of H2pdc (167 mg, 1 mmol), Co(CH3COO)2·4H2O (125 mg, 0.5 mmol) and CaCl2 (110 mg, 1 mmol) in 15 ml of distilled H2O was stirred for 10 min in air. 0.5 M NaOH was added dropwise and the mixture was turned into a Parr Teflon-lined stainless steel vessel and heated at 423 K for 3 d. Blue [purple in CIF?] block-shaped crystals of 1 were obtained in a yield of 70% (based on pyridine-2,6-di­carb­oxy­lic acid).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The H atoms of the n class="Chemical">water mol­ecules were located from difference-Fourier maps and refined with distance restraints: O—H = 0.85 (1) Å, H⋯H = 1.34 (1) Å with U iso(H) = 1.5U eq(O). C-bound H atoms atoms were included in calculated positions and refined as riding: C—H = 0.93 Å with U iso(H) = 1.2U eq(C).

Table 3

Experimental details

Crystal data
Chemical formula	[CaCo(C7H3NO4)2(H2O)4]·2H2O
M r	537.31
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c (Å)	8.6299 (8), 8.7781 (8), 14.0726 (12)
α, β, γ (°)	80.683 (1), 73.602 (1), 89.568 (1)
V (Å3)	1008.38 (16)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.18
Crystal size (mm)	0.35 × 0.33 × 0.33
Data collection
Diffractometer	Bruker SMART CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	7052, 3537, 3342
R int	0.012
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.023, 0.064, 1.01
No. of reflections	3537
No. of parameters	326
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.44, −0.49

Computer programs: APEX2 and SAINT (Bruker, 2009 ▸), SHELXS97 and SHELXTL (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), Mercury (Macrae et al., 2008 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) 1, global. DOI: 10.1107/S2056989018007120/xu5921sup1.cif

CCDC reference: 1832782

Additional supporting information: crystallographic information; 3D view; checkCIF report

[CaCo(C7H3NO4)2(H2O)4]·2H2O	Z = 2
Mr = 537.31	F(000) = 550
Triclinic, P1	Dx = 1.770 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6299 (8) Å	Cell parameters from 5842 reflections
b = 8.7781 (8) Å	θ = 2.4–27.7°
c = 14.0726 (12) Å	µ = 1.18 mm−1
α = 80.683 (1)°	T = 296 K
β = 73.602 (1)°	Block, purple
γ = 89.568 (1)°	0.35 × 0.33 × 0.33 mm
V = 1008.38 (16) Å3

Bruker SMART CCD diffractometer	3342 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.012
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
φ and ω scans	h = −10→10
7052 measured reflections	k = −10→9
3537 independent reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.064	w = 1/[σ2(Fo2) + (0.0385P)2 + 0.4728P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
3537 reflections	Δρmax = 0.44 e Å−3
326 parameters	Δρmin = −0.49 e Å−3
18 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0300 (14)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
Co1	0.39269 (3)	0.14153 (3)	0.252249 (15)	0.02155 (10)
Ca1	0.86691 (4)	−0.38042 (3)	0.24956 (2)	0.01922 (10)
O1	0.24638 (15)	0.02836 (14)	0.18004 (9)	0.0291 (3)
O2	0.20443 (16)	0.02565 (16)	0.03080 (10)	0.0364 (3)
O3	0.55173 (16)	0.32701 (14)	0.25445 (9)	0.0301 (3)
O4	0.73160 (16)	0.50764 (15)	0.15426 (11)	0.0351 (3)
O5	0.19108 (15)	0.25552 (15)	0.33569 (9)	0.0308 (3)
O6	0.02552 (14)	0.25623 (14)	0.48985 (9)	0.0297 (3)
O7	0.57745 (15)	−0.03428 (14)	0.24055 (9)	0.0295 (3)
O8	0.63798 (15)	−0.25231 (14)	0.32698 (10)	0.0325 (3)
N1	0.47499 (16)	0.24083 (15)	0.10671 (10)	0.0192 (3)
N2	0.33969 (16)	0.01759 (15)	0.39227 (10)	0.0192 (3)
C1	0.42012 (19)	0.18591 (18)	0.03843 (12)	0.0200 (3)
C2	0.4907 (2)	0.23423 (19)	−0.06355 (12)	0.0247 (4)
H2A	0.4515	0.1975	−0.1111	0.030*
C3	0.6221 (2)	0.3394 (2)	−0.09255 (13)	0.0280 (4)
H3A	0.6739	0.3713	−0.1604	0.034*
C4	0.6763 (2)	0.3971 (2)	−0.02081 (13)	0.0263 (4)
H4A	0.7631	0.4685	−0.0397	0.032*
C5	0.59765 (19)	0.34531 (18)	0.07952 (12)	0.0209 (3)
C6	0.27915 (19)	0.06991 (19)	0.08568 (12)	0.0226 (3)
C7	0.6325 (2)	0.39819 (19)	0.16942 (13)	0.0237 (4)
C8	0.22421 (19)	0.06489 (18)	0.46591 (12)	0.0194 (3)
C9	0.1926 (2)	−0.0107 (2)	0.56454 (12)	0.0236 (4)
H9A	0.1131	0.0227	0.6159	0.028*
C10	0.2824 (2)	−0.13715 (19)	0.58450 (12)	0.0251 (4)
H10A	0.2628	−0.1901	0.6498	0.030*
C11	0.4018 (2)	−0.18510 (19)	0.50709 (12)	0.0232 (3)
H11A	0.4627	−0.2698	0.5197	0.028*
C12	0.42759 (19)	−0.10363 (18)	0.41099 (12)	0.0200 (3)
C13	0.13795 (19)	0.20400 (19)	0.42944 (12)	0.0216 (3)
C14	0.55835 (19)	−0.13350 (19)	0.31863 (12)	0.0222 (3)
OW1	0.95691 (18)	−0.19898 (17)	0.10151 (11)	0.0404 (3)
OW2	1.02789 (16)	−0.59450 (15)	0.21033 (10)	0.0319 (3)
OW3	1.06339 (17)	−0.23885 (16)	0.29216 (10)	0.0354 (3)
OW4	0.84002 (17)	−0.51094 (15)	0.41287 (9)	0.0325 (3)
OW5	0.6149 (3)	−0.4991 (2)	0.59299 (15)	0.0782 (7)
OW6	0.8857 (2)	−0.8525 (2)	0.16230 (15)	0.0604 (5)
HW1A	1.039 (2)	−0.139 (3)	0.080 (2)	0.091*
HW4A	0.902 (3)	−0.577 (3)	0.430 (2)	0.091*
HW3A	1.126 (3)	−0.163 (2)	0.2603 (17)	0.091*
HW4B	0.771 (3)	−0.499 (3)	0.4666 (13)	0.091*
HW3B	1.060 (4)	−0.247 (3)	0.3528 (8)	0.091*
HW1B	0.898 (3)	−0.168 (3)	0.0638 (19)	0.091*
HW2A	0.985 (4)	−0.668 (2)	0.192 (2)	0.091*
HW2B	1.072 (3)	−0.639 (3)	0.2531 (18)	0.091*
HW6A	0.7978 (18)	−0.902 (3)	0.172 (2)	0.091*
HW5B	0.596 (4)	−0.447 (3)	0.6408 (17)	0.091*
HW6B	0.958 (2)	−0.907 (3)	0.134 (2)	0.091*
HW5A	0.539 (3)	−0.569 (3)	0.613 (2)	0.091*

	U11	U22	U33	U12	U13	U23
Co1	0.02474 (14)	0.02310 (14)	0.01634 (14)	0.00250 (9)	−0.00629 (9)	−0.00120 (9)
Ca1	0.01825 (18)	0.01797 (18)	0.02199 (19)	0.00136 (13)	−0.00637 (13)	−0.00374 (13)
O1	0.0303 (7)	0.0314 (7)	0.0239 (6)	−0.0101 (5)	−0.0077 (5)	0.0011 (5)
O2	0.0394 (7)	0.0394 (8)	0.0349 (7)	−0.0162 (6)	−0.0220 (6)	0.0022 (6)
O3	0.0390 (7)	0.0304 (7)	0.0253 (7)	−0.0001 (6)	−0.0148 (6)	−0.0069 (5)
O4	0.0356 (7)	0.0294 (7)	0.0482 (8)	−0.0055 (6)	−0.0228 (6)	−0.0095 (6)
O5	0.0333 (7)	0.0340 (7)	0.0240 (6)	0.0140 (6)	−0.0087 (5)	−0.0014 (5)
O6	0.0273 (6)	0.0335 (7)	0.0293 (7)	0.0119 (5)	−0.0074 (5)	−0.0094 (5)
O7	0.0306 (7)	0.0314 (7)	0.0226 (6)	0.0071 (5)	−0.0027 (5)	−0.0022 (5)
O8	0.0291 (7)	0.0267 (7)	0.0385 (7)	0.0121 (5)	−0.0044 (6)	−0.0060 (6)
N1	0.0195 (7)	0.0200 (7)	0.0191 (7)	0.0001 (5)	−0.0077 (5)	−0.0025 (5)
N2	0.0193 (7)	0.0200 (7)	0.0193 (7)	0.0026 (5)	−0.0068 (5)	−0.0038 (5)
C1	0.0203 (8)	0.0204 (8)	0.0210 (8)	0.0017 (6)	−0.0089 (6)	−0.0035 (6)
C2	0.0296 (9)	0.0265 (9)	0.0205 (8)	0.0037 (7)	−0.0098 (7)	−0.0059 (7)
C3	0.0274 (9)	0.0317 (10)	0.0199 (8)	0.0013 (7)	−0.0005 (7)	−0.0008 (7)
C4	0.0204 (8)	0.0240 (9)	0.0314 (9)	−0.0025 (7)	−0.0042 (7)	−0.0014 (7)
C5	0.0181 (8)	0.0191 (8)	0.0265 (8)	0.0016 (6)	−0.0086 (6)	−0.0034 (6)
C6	0.0212 (8)	0.0206 (8)	0.0276 (9)	0.0003 (7)	−0.0096 (7)	−0.0033 (7)
C7	0.0227 (8)	0.0212 (8)	0.0328 (10)	0.0056 (7)	−0.0152 (7)	−0.0079 (7)
C8	0.0178 (7)	0.0214 (8)	0.0206 (8)	0.0005 (6)	−0.0067 (6)	−0.0059 (6)
C9	0.0230 (8)	0.0276 (9)	0.0198 (8)	0.0004 (7)	−0.0046 (7)	−0.0051 (7)
C10	0.0296 (9)	0.0252 (9)	0.0199 (8)	−0.0034 (7)	−0.0086 (7)	0.0010 (7)
C11	0.0256 (8)	0.0186 (8)	0.0268 (9)	0.0016 (7)	−0.0109 (7)	−0.0012 (7)
C12	0.0195 (8)	0.0180 (8)	0.0239 (8)	0.0007 (6)	−0.0076 (6)	−0.0050 (6)
C13	0.0206 (8)	0.0230 (8)	0.0244 (8)	0.0025 (7)	−0.0096 (7)	−0.0074 (7)
C14	0.0203 (8)	0.0215 (8)	0.0261 (9)	0.0011 (7)	−0.0073 (7)	−0.0069 (7)
OW1	0.0403 (8)	0.0436 (8)	0.0358 (8)	−0.0165 (7)	−0.0177 (6)	0.0116 (6)
OW2	0.0345 (7)	0.0307 (7)	0.0338 (7)	0.0123 (6)	−0.0144 (6)	−0.0069 (6)
OW3	0.0389 (8)	0.0386 (8)	0.0292 (7)	−0.0145 (6)	−0.0115 (6)	−0.0036 (6)
OW4	0.0392 (8)	0.0295 (7)	0.0255 (7)	0.0071 (6)	−0.0057 (6)	−0.0014 (5)
OW5	0.0881 (15)	0.0622 (12)	0.0629 (12)	−0.0295 (10)	0.0275 (10)	−0.0355 (10)
OW6	0.0414 (9)	0.0520 (10)	0.0866 (13)	−0.0007 (8)	−0.0021 (9)	−0.0370 (9)

Co1—N1	2.0172 (13)	C2—H2A	0.9300
Co1—N2	2.0199 (13)	C3—C4	1.389 (3)
Co1—O5	2.1466 (12)	C3—H3A	0.9300
Co1—O3	2.1469 (13)	C4—C5	1.384 (2)
Co1—O1	2.1643 (12)	C4—H4A	0.9300
Co1—O7	2.2018 (12)	C5—C7	1.521 (2)
Ca1—O4i	2.3358 (12)	C8—C9	1.390 (2)
Ca1—OW4	2.3449 (13)	C8—C13	1.519 (2)
Ca1—O8	2.3458 (12)	C9—C10	1.386 (2)
Ca1—OW1	2.3476 (13)	C9—H9A	0.9300
Ca1—OW3	2.3719 (13)	C10—C11	1.390 (2)
Ca1—OW2	2.3727 (12)	C10—H10A	0.9300
O1—C6	1.268 (2)	C11—C12	1.382 (2)
O2—C6	1.243 (2)	C11—H11A	0.9300
O3—C7	1.266 (2)	C12—C14	1.520 (2)
O4—C7	1.242 (2)	OW1—HW1A	0.844 (10)
O4—Ca1ii	2.3358 (12)	OW1—HW1B	0.846 (10)
O5—C13	1.274 (2)	OW2—HW2A	0.849 (10)
O6—C13	1.236 (2)	OW2—HW2B	0.845 (10)
O7—C14	1.258 (2)	OW3—HW3A	0.838 (10)
O8—C14	1.253 (2)	OW3—HW3B	0.837 (10)
N1—C5	1.334 (2)	OW4—HW4A	0.840 (10)
N1—C1	1.338 (2)	OW4—HW4B	0.842 (10)
N2—C8	1.338 (2)	OW5—HW5B	0.854 (10)
N2—C12	1.337 (2)	OW5—HW5A	0.854 (10)
C1—C2	1.387 (2)	OW6—HW6A	0.843 (10)
C1—C6	1.517 (2)	OW6—HW6B	0.839 (10)
C2—C3	1.392 (3)
N1—Co1—N2	170.56 (5)	C4—C3—H3A	119.8
N1—Co1—O5	113.11 (5)	C2—C3—H3A	119.8
N2—Co1—O5	76.33 (5)	C5—C4—C3	118.16 (16)
N1—Co1—O3	76.31 (5)	C5—C4—H4A	120.9
N2—Co1—O3	104.44 (5)	C3—C4—H4A	120.9
O5—Co1—O3	89.74 (5)	N1—C5—C4	120.99 (15)
N1—Co1—O1	76.52 (5)	N1—C5—C7	112.31 (14)
N2—Co1—O1	103.75 (5)	C4—C5—C7	126.69 (15)
O5—Co1—O1	93.20 (5)	O2—C6—O1	125.55 (15)
O3—Co1—O1	151.54 (5)	O2—C6—C1	118.66 (15)
N1—Co1—O7	94.39 (5)	O1—C6—C1	115.77 (14)
N2—Co1—O7	76.18 (5)	O4—C7—O3	125.91 (16)
O5—Co1—O7	152.44 (5)	O4—C7—C5	118.68 (16)
O3—Co1—O7	95.18 (5)	O3—C7—C5	115.38 (14)
O1—Co1—O7	95.16 (5)	N2—C8—C9	120.75 (15)
O4i—Ca1—OW4	116.69 (5)	N2—C8—C13	113.26 (13)
O4i—Ca1—O8	92.96 (5)	C9—C8—C13	126.00 (14)
OW4—Ca1—O8	84.24 (5)	C10—C9—C8	118.39 (15)
O4i—Ca1—OW1	82.87 (5)	C10—C9—H9A	120.8
OW4—Ca1—OW1	160.32 (5)	C8—C9—H9A	120.8
O8—Ca1—OW1	97.60 (5)	C9—C10—C11	120.17 (15)
O4i—Ca1—OW3	160.85 (5)	C9—C10—H10A	119.9
OW4—Ca1—OW3	80.10 (5)	C11—C10—H10A	119.9
O8—Ca1—OW3	98.14 (5)	C12—C11—C10	118.30 (15)
OW1—Ca1—OW3	80.24 (5)	C12—C11—H11A	120.8
O4i—Ca1—OW2	78.31 (5)	C10—C11—H11A	120.8
OW4—Ca1—OW2	80.75 (5)	N2—C12—C11	121.15 (15)
O8—Ca1—OW2	156.81 (5)	N2—C12—C14	113.20 (14)
OW1—Ca1—OW2	102.49 (5)	C11—C12—C14	125.58 (14)
OW3—Ca1—OW2	96.57 (5)	O6—C13—O5	125.96 (15)
C6—O1—Co1	115.23 (10)	O6—C13—C8	119.55 (15)
C7—O3—Co1	115.79 (10)	O5—C13—C8	114.48 (14)
C7—O4—Ca1ii	136.36 (12)	O8—C14—O7	126.01 (15)
C13—O5—Co1	116.59 (10)	O8—C14—C12	117.73 (15)
C14—O7—Co1	114.36 (10)	O7—C14—C12	116.25 (14)
C14—O8—Ca1	144.69 (12)	Ca1—OW1—HW1A	131.0 (19)
C5—N1—C1	121.46 (14)	Ca1—OW1—HW1B	123.2 (19)
C5—N1—Co1	118.88 (11)	HW1A—OW1—HW1B	104.7 (15)
C1—N1—Co1	119.07 (11)	Ca1—OW2—HW2A	117 (2)
C8—N2—C12	121.24 (14)	Ca1—OW2—HW2B	118 (2)
C8—N2—Co1	119.12 (11)	HW2A—OW2—HW2B	104.6 (15)
C12—N2—Co1	119.49 (11)	Ca1—OW3—HW3A	132.0 (19)
N1—C1—C2	120.97 (15)	Ca1—OW3—HW3B	118.4 (19)
N1—C1—C6	112.71 (14)	HW3A—OW3—HW3B	108.0 (15)
C2—C1—C6	126.33 (15)	Ca1—OW4—HW4A	126.5 (19)
C1—C2—C3	117.92 (15)	Ca1—OW4—HW4B	128.2 (18)
C1—C2—H2A	121.0	HW4A—OW4—HW4B	105.2 (15)
C3—C2—H2A	121.0	HW5B—OW5—HW5A	103.9 (15)
C4—C3—C2	120.46 (16)	HW6A—OW6—HW6B	105.7 (15)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1A···O2iii	0.84 (1)	1.93 (1)	2.769 (2)	171 (3)
OW1—HW1B···O2iv	0.85 (1)	2.06 (1)	2.870 (2)	161 (3)
OW2—HW2A···OW6	0.85 (1)	2.00 (1)	2.846 (2)	175 (3)
OW2—HW2B···O5v	0.85 (1)	1.89 (1)	2.730 (2)	173 (3)
OW3—HW3A···O1iii	0.84 (1)	1.99 (1)	2.817 (2)	172 (3)
OW3—HW3B···O6vi	0.84 (1)	2.12 (1)	2.923 (2)	162 (3)
OW4—HW4A···O6v	0.84 (1)	2.02 (1)	2.851 (2)	172 (3)
OW4—HW4B···OW5	0.84 (1)	1.90 (1)	2.741 (2)	173 (3)
OW5—HW5A···O8vii	0.85 (1)	2.10 (1)	2.946 (2)	174 (3)
OW5—HW5B···O3vi	0.85 (1)	2.08 (2)	2.870 (2)	153 (3)
OW6—HW6A···O7i	0.84 (1)	2.13 (1)	2.945 (2)	163 (3)
OW6—HW6B···O2v	0.84 (1)	2.34 (1)	3.140 (2)	160 (3)
C2—H2A···O7iv	0.93	2.56	3.448 (2)	160
C10—H10A···O3vi	0.93	2.55	3.246 (2)	132