A novel three-dimensional tetra­nuclear Co^II coordination polymer with water hexa­mers based on the V-shaped tetra­carboxyl­ate ligand 4-(2,4-di­carb­oxylato­phen­oxy)phthalate

A new coordination polymer (CP), namely, poly[[di­aqua­tris­[μ₂-1,4-bis­(1H-imidazol-1-yl)benzene]bis­[μ₆-4-(2,4-di­carboxyl­atophen­oxy)phthalato]tetra­co­balt(II)] hexa­hydrate], {[Co₄(C₁₆H₆O₉)₂(C₁₂H₁₀N₄)₃(H₂O)₂]·6H₂O}_n, has been synthesized by solvothermal reaction. The CP was fully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. It presents a three-dimensional (3D) structure based on tetra­nuclear Co^II secondary building units (SBUs) with a tfz-d net and point symbol (4³)₂(4⁶·6¹⁸·8⁴). The 4-(2,4-di­carb­oxy­phen­oxy)phthalic acid (H₄dcppa) ligands are com­pletely deprotonated and link {Co₄(COO)₄}⁴⁻ SBUs into two-dimensional (2D) layers. Furthermore, adjacent layers are connected by 1,4-bis­(1H-imidazol-1-yl)benzene (bib) ligands, giving rise to a 3D supra­molecular architecture. Inter­estingly, there are numerous elliptical cavities in the CP where isolated unique discrete hexa­meric water clusters have been observed. The results of thermogravimetric and magnetic analyses are described in detail.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: pubCIF (Westrip, 2010).

Poly[[diaquatris[µ₂-1,4-bis(1H-imidazol-1-yl)benzene]bis[µ₆-4-(2,4-dicarboxylatophenoxy)phthalato]tetracobalt(II)] hexahydrate]

Crystal data

[Co4(C16H6O9)2(C12H10N4)3(H2O)2]·6H2O	Z = 1
Mr = 1694.98	F(000) = 866
Triclinic, P1	Dx = 1.705 Mg m^−3
a = 10.660 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.240 (2) Å	Cell parameters from 9770 reflections
c = 14.649 (3) Å	θ = 3.0–43.1°
α = 109.48 (3)°	µ = 1.09 mm^−1
β = 107.32 (3)°	T = 200 K
γ = 98.87 (3)°	Block, purple
V = 1650.6 (7) Å^3	0.20 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer	4994 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2012)	θmax = 25.5°, θmin = 3.0°
Tmin = 0.670, Tmax = 0.746	h = −12→12
18817 measured reflections	k = −14→14
6077 independent reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.050P)^2 + 1.3022P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
6077 reflections	Δρmax = 0.43 e Å^−3
496 parameters	Δρmin = −0.40 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.30220 (3)	0.91106 (3)	0.44303 (2)	0.01483 (10)
Co2	0.03427 (3)	0.59524 (3)	0.21886 (3)	0.01792 (11)
C1	−0.0100 (3)	0.5924 (2)	0.6859 (2)	0.0207 (6)
C2	−0.0542 (3)	0.6032 (2)	0.58218 (19)	0.0172 (5)
C3	0.0289 (3)	0.6830 (2)	0.5610 (2)	0.0180 (6)
H3	0.113147	0.735558	0.614728	0.022*
C4	−0.1783 (3)	0.5287 (3)	0.5047 (2)	0.0220 (6)
H4	−0.235663	0.473281	0.517961	0.026*
C5	−0.2191 (3)	0.5347 (3)	0.4078 (2)	0.0218 (6)
H5	−0.305520	0.485132	0.355426	0.026*
C6	0.0891 (2)	0.7730 (2)	0.44338 (19)	0.0170 (5)
C7	−0.0082 (3)	0.6882 (2)	0.46237 (19)	0.0150 (5)
C8	−0.1338 (2)	0.6131 (2)	0.38727 (19)	0.0157 (5)
C9	−0.3034 (2)	0.6320 (2)	0.25411 (19)	0.0172 (5)
C10	−0.4027 (3)	0.5489 (3)	0.1625 (2)	0.0251 (6)
H10	−0.383140	0.481731	0.119423	0.030*
C11	−0.3300 (3)	0.7325 (2)	0.31297 (19)	0.0187 (6)
H11	−0.258127	0.792358	0.373777	0.022*
C12	−0.5333 (3)	0.5647 (3)	0.1338 (2)	0.0251 (6)
H12	−0.602710	0.507628	0.070059	0.030*
C13	−0.5647 (3)	0.6613 (2)	0.19548 (19)	0.0182 (6)
C14	−0.7146 (3)	0.6614 (2)	0.16267 (19)	0.0202 (6)
C15	−0.4601 (2)	0.7481 (2)	0.28507 (19)	0.0165 (5)
C16	−0.4850 (3)	0.8560 (2)	0.35692 (19)	0.0185 (6)
C17	0.4719 (3)	0.8334 (3)	0.6131 (2)	0.0265 (6)
H17	0.475133	0.903541	0.668145	0.032*
C18	0.4266 (3)	0.6993 (3)	0.4615 (2)	0.0241 (6)
H18	0.389400	0.655655	0.387795	0.029*
C19	0.5073 (3)	0.6643 (3)	0.5305 (2)	0.0273 (6)
H19	0.539183	0.594602	0.514564	0.033*
C20	0.6024 (3)	0.7430 (3)	0.7259 (2)	0.0243 (6)
C21	0.5676 (4)	0.7971 (4)	0.8094 (3)	0.0554 (12)
H21	0.499368	0.838685	0.802341	0.066*
C22	0.6976 (3)	0.6793 (3)	0.7356 (2)	0.0341 (8)
H22	0.719498	0.639313	0.677109	0.041*
C23	0.7618 (3)	0.6734 (3)	0.8305 (2)	0.0342 (8)
H23	0.827646	0.629361	0.836967	0.041*
C24	0.6320 (4)	0.7911 (4)	0.9040 (3)	0.0529 (12)
H24	0.607907	0.828811	0.961830	0.063*
C25	0.7304 (3)	0.7309 (3)	0.9149 (2)	0.0233 (6)
C26	0.8743 (3)	0.6556 (3)	1.0365 (2)	0.0243 (6)
H26	0.885924	0.590813	0.984890	0.029*
C27	0.8075 (3)	0.8106 (3)	1.1090 (2)	0.0255 (6)
H27	0.765512	0.874431	1.119897	0.031*
C28	0.8865 (3)	0.7817 (3)	1.1830 (2)	0.0227 (6)
H28	0.909486	0.822821	1.255908	0.027*
C29	0.1245 (4)	1.0731 (3)	0.3724 (2)	0.0369 (8)
H29	0.118484	1.109689	0.438638	0.044*
C30	0.1787 (3)	0.9647 (3)	0.2509 (2)	0.0202 (6)
H30	0.217254	0.909329	0.213261	0.024*
C31	0.0625 (4)	1.0938 (3)	0.2873 (2)	0.0373 (8)
H31	0.005451	1.145751	0.282588	0.045*
C32	0.0493 (3)	1.0126 (2)	0.1028 (2)	0.0200 (6)
C33	−0.0337 (4)	1.0785 (4)	0.0724 (2)	0.0462 (10)
H33	−0.057586	1.134163	0.122676	0.055*
C34	0.0837 (4)	0.9341 (4)	0.0304 (2)	0.0455 (10)
H34	0.142101	0.887919	0.050205	0.055*
N1	0.1971 (2)	0.9920 (2)	0.34967 (16)	0.0201 (5)
N2	0.0983 (2)	1.0248 (2)	0.20923 (16)	0.0200 (5)
N3	0.9291 (2)	0.6840 (2)	1.13778 (17)	0.0213 (5)
N4	0.7996 (2)	0.7300 (2)	1.01520 (17)	0.0222 (5)
N5	0.5339 (2)	0.7490 (2)	0.62770 (17)	0.0234 (5)
N6	0.4067 (2)	0.8069 (2)	0.51355 (17)	0.0217 (5)
O1	0.10754 (18)	0.74515 (17)	0.35744 (13)	0.0202 (4)
O2	0.1578 (2)	0.87173 (18)	0.51617 (15)	0.0270 (5)
O3	0.0882 (2)	0.6725 (2)	0.76095 (15)	0.0386 (6)
O4	−0.0777 (2)	0.50101 (18)	0.68987 (14)	0.0238 (4)
O5	−0.17302 (18)	0.61484 (18)	0.28813 (13)	0.0201 (4)
O6	−0.38212 (19)	0.92876 (17)	0.43352 (15)	0.0268 (5)
O7	−0.60595 (18)	0.86303 (17)	0.33693 (13)	0.0206 (4)
O8	−0.78526 (19)	0.60515 (19)	0.19749 (16)	0.0279 (5)
O9	−0.7578 (2)	0.7078 (2)	0.09995 (15)	0.0304 (5)
O10	−0.0748 (2)	0.4250 (2)	0.10086 (16)	0.0428 (6)
H10A	−0.129572	0.393769	0.039755	0.064*
H10B	−0.093545	0.381313	0.130602	0.064*
O11	0.6804 (4)	0.0037 (3)	0.2479 (3)	0.0871 (11)
H11A	0.692303	0.054983	0.219666	0.131*
H11B	0.743095	0.036922	0.322513	0.131*
O12	0.6856 (4)	0.1270 (4)	0.1235 (3)	0.1001 (13)
H12A	0.644116	0.124202	0.065032	0.150*
H12B	0.743591	0.193694	0.157552	0.150*
O13	0.4309 (4)	0.8697 (4)	0.0737 (4)	0.1225 (17)
H13A	0.378425	0.816711	0.079903	0.184*
H13B	0.483745	0.914783	0.133583	0.184*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01526 (18)	0.01582 (19)	0.01129 (17)	0.00376 (14)	0.00155 (13)	0.00624 (14)
Co2	0.01805 (19)	0.0214 (2)	0.01406 (18)	0.00587 (15)	0.00301 (14)	0.00941 (16)
C1	0.0289 (14)	0.0214 (15)	0.0209 (14)	0.0143 (12)	0.0144 (12)	0.0115 (12)
C2	0.0240 (13)	0.0185 (13)	0.0167 (12)	0.0128 (11)	0.0112 (11)	0.0099 (11)
C3	0.0192 (13)	0.0191 (14)	0.0162 (12)	0.0070 (11)	0.0059 (10)	0.0077 (11)
C4	0.0225 (14)	0.0250 (15)	0.0267 (14)	0.0075 (12)	0.0143 (12)	0.0151 (13)
C5	0.0161 (13)	0.0281 (15)	0.0213 (14)	0.0042 (11)	0.0055 (11)	0.0123 (12)
C6	0.0149 (12)	0.0217 (14)	0.0185 (13)	0.0087 (11)	0.0057 (10)	0.0121 (12)
C7	0.0188 (12)	0.0158 (13)	0.0150 (12)	0.0083 (10)	0.0093 (10)	0.0076 (11)
C8	0.0162 (12)	0.0216 (14)	0.0155 (12)	0.0108 (11)	0.0076 (10)	0.0111 (11)
C9	0.0115 (12)	0.0275 (15)	0.0164 (12)	0.0060 (11)	0.0048 (10)	0.0136 (12)
C10	0.0212 (14)	0.0264 (15)	0.0223 (14)	0.0080 (12)	0.0059 (12)	0.0048 (13)
C11	0.0150 (12)	0.0227 (15)	0.0117 (12)	0.0010 (11)	−0.0001 (10)	0.0055 (11)
C12	0.0184 (13)	0.0274 (16)	0.0168 (13)	0.0039 (12)	0.0006 (11)	0.0003 (12)
C13	0.0160 (12)	0.0242 (14)	0.0144 (12)	0.0056 (11)	0.0045 (10)	0.0090 (11)
C14	0.0191 (13)	0.0210 (14)	0.0107 (12)	0.0036 (11)	0.0005 (10)	−0.0001 (11)
C15	0.0152 (12)	0.0182 (13)	0.0152 (12)	0.0042 (10)	0.0037 (10)	0.0079 (11)
C16	0.0226 (14)	0.0202 (14)	0.0139 (12)	0.0058 (11)	0.0051 (11)	0.0099 (11)
C17	0.0324 (16)	0.0293 (16)	0.0210 (14)	0.0167 (13)	0.0079 (12)	0.0123 (13)
C18	0.0311 (15)	0.0219 (15)	0.0176 (13)	0.0046 (12)	0.0057 (12)	0.0099 (12)
C19	0.0383 (17)	0.0197 (15)	0.0226 (14)	0.0106 (13)	0.0079 (13)	0.0090 (12)
C20	0.0277 (15)	0.0301 (16)	0.0179 (13)	0.0144 (13)	0.0046 (12)	0.0136 (12)
C21	0.072 (3)	0.089 (3)	0.0318 (18)	0.069 (3)	0.0224 (18)	0.034 (2)
C22	0.0457 (19)	0.046 (2)	0.0185 (14)	0.0296 (16)	0.0118 (13)	0.0153 (14)
C23	0.0431 (18)	0.045 (2)	0.0242 (15)	0.0324 (16)	0.0117 (14)	0.0177 (15)
C24	0.069 (3)	0.090 (3)	0.0248 (17)	0.062 (2)	0.0250 (17)	0.0283 (19)
C25	0.0233 (14)	0.0298 (16)	0.0193 (14)	0.0115 (12)	0.0033 (11)	0.0152 (13)
C26	0.0273 (15)	0.0293 (16)	0.0192 (13)	0.0140 (12)	0.0066 (12)	0.0124 (12)
C27	0.0332 (16)	0.0267 (16)	0.0202 (14)	0.0145 (13)	0.0097 (12)	0.0110 (13)
C28	0.0260 (14)	0.0257 (15)	0.0173 (13)	0.0074 (12)	0.0083 (11)	0.0096 (12)
C29	0.055 (2)	0.042 (2)	0.0154 (14)	0.0297 (17)	0.0094 (14)	0.0093 (14)
C30	0.0214 (13)	0.0249 (15)	0.0174 (13)	0.0119 (11)	0.0050 (11)	0.0117 (12)
C31	0.056 (2)	0.0404 (19)	0.0227 (15)	0.0377 (17)	0.0131 (15)	0.0125 (14)
C32	0.0212 (13)	0.0208 (14)	0.0161 (12)	0.0073 (11)	0.0019 (10)	0.0090 (11)
C33	0.070 (2)	0.063 (3)	0.0202 (15)	0.052 (2)	0.0181 (16)	0.0194 (17)
C34	0.067 (2)	0.065 (2)	0.0241 (16)	0.055 (2)	0.0167 (16)	0.0259 (17)
N1	0.0229 (11)	0.0214 (12)	0.0148 (11)	0.0079 (10)	0.0038 (9)	0.0078 (10)
N2	0.0261 (12)	0.0208 (12)	0.0155 (11)	0.0113 (10)	0.0053 (9)	0.0103 (10)
N3	0.0213 (11)	0.0267 (13)	0.0176 (11)	0.0080 (10)	0.0050 (9)	0.0125 (10)
N4	0.0249 (12)	0.0275 (13)	0.0167 (11)	0.0124 (10)	0.0052 (9)	0.0121 (10)
N5	0.0281 (12)	0.0265 (13)	0.0184 (11)	0.0142 (10)	0.0048 (10)	0.0130 (10)
N6	0.0236 (12)	0.0260 (13)	0.0195 (11)	0.0105 (10)	0.0053 (9)	0.0149 (10)
O1	0.0231 (9)	0.0215 (10)	0.0165 (9)	0.0045 (8)	0.0074 (8)	0.0091 (8)
O2	0.0305 (11)	0.0228 (11)	0.0220 (10)	−0.0001 (9)	0.0109 (9)	0.0046 (9)
O3	0.0521 (14)	0.0335 (13)	0.0184 (10)	−0.0036 (11)	0.0030 (10)	0.0122 (10)
O4	0.0312 (10)	0.0263 (11)	0.0204 (10)	0.0101 (9)	0.0102 (8)	0.0159 (9)
O5	0.0165 (9)	0.0336 (11)	0.0163 (9)	0.0115 (8)	0.0071 (7)	0.0145 (8)
O6	0.0233 (10)	0.0207 (10)	0.0221 (10)	0.0016 (8)	0.0024 (8)	−0.0009 (9)
O7	0.0207 (9)	0.0281 (11)	0.0151 (9)	0.0136 (8)	0.0057 (7)	0.0091 (8)
O8	0.0195 (10)	0.0319 (12)	0.0377 (12)	0.0088 (9)	0.0138 (9)	0.0169 (10)
O9	0.0234 (10)	0.0449 (13)	0.0205 (10)	0.0104 (9)	0.0009 (8)	0.0164 (10)
O10	0.0588 (15)	0.0302 (13)	0.0197 (11)	−0.0052 (11)	−0.0030 (10)	0.0099 (10)
O11	0.112 (3)	0.078 (2)	0.067 (2)	0.032 (2)	0.041 (2)	0.0160 (19)
O12	0.069 (2)	0.109 (3)	0.115 (3)	0.000 (2)	0.037 (2)	0.044 (3)
O13	0.086 (3)	0.142 (4)	0.144 (4)	−0.005 (3)	0.021 (3)	0.100 (3)

Geometric parameters (Å, º)

Co1—O6^i	2.011 (2)	C18—N6	1.369 (4)
Co1—O7^ii	2.0479 (19)	C18—H18	0.9500
Co1—N1	2.107 (2)	C19—N5	1.366 (4)
Co1—N6	2.137 (2)	C19—H19	0.9500
Co1—O2	2.202 (2)	C20—C21	1.370 (4)
Co1—O1	2.336 (2)	C20—C22	1.374 (4)
Co2—O8^ii	2.031 (2)	C20—N5	1.439 (3)
Co2—O1	2.056 (2)	C21—C24	1.384 (4)
Co2—O4^iii	2.059 (2)	C21—H21	0.9500
Co2—N3^iv	2.072 (2)	C22—C23	1.387 (4)
Co2—O10	2.082 (2)	C22—H22	0.9500
C1—O3	1.243 (4)	C23—C25	1.370 (4)
C1—O4	1.263 (3)	C23—H23	0.9500
C1—C2	1.508 (4)	C24—C25	1.372 (4)
C2—C4	1.383 (4)	C24—H24	0.9500
C2—C3	1.391 (4)	C25—N4	1.439 (3)
C3—C7	1.406 (4)	C26—N3	1.319 (3)
C3—H3	0.9500	C26—N4	1.351 (4)
C4—C5	1.387 (4)	C26—H26	0.9500
C4—H4	0.9500	C27—C28	1.346 (4)
C5—C8	1.387 (4)	C27—N4	1.368 (4)
C5—H5	0.9500	C27—H27	0.9500
C6—O2	1.239 (3)	C28—N3	1.376 (4)
C6—O1	1.274 (3)	C28—H28	0.9500
C6—C7	1.504 (4)	C29—C31	1.352 (4)
C7—C8	1.385 (4)	C29—N1	1.366 (4)
C8—O5	1.395 (3)	C29—H29	0.9500
C9—C10	1.366 (4)	C30—N1	1.317 (3)
C9—C11	1.372 (4)	C30—N2	1.354 (3)
C9—O5	1.404 (3)	C30—H30	0.9500
C10—C12	1.393 (4)	C31—N2	1.372 (4)
C10—H10	0.9500	C31—H31	0.9500
C11—C15	1.387 (3)	C32—C34	1.357 (4)
C11—H11	0.9500	C32—C33	1.363 (4)
C12—C13	1.384 (4)	C32—N2	1.436 (3)
C12—H12	0.9500	C33—C34^v	1.384 (4)
C13—C15	1.389 (4)	C33—H33	0.9500
C13—C14	1.526 (4)	C34—H34	0.9500
C14—O9	1.247 (3)	O10—H10A	0.8245
C14—O8	1.267 (3)	O10—H10B	0.8305
C15—C16	1.507 (4)	O11—H11A	0.8725
C16—O6	1.247 (3)	O11—H11B	0.9956
C16—O7	1.258 (3)	O12—H12A	0.8251
C17—N6	1.313 (3)	O12—H12B	0.8284
C17—N5	1.350 (4)	O13—H13A	0.8362
C17—H17	0.9500	O13—H13B	0.8241
C18—C19	1.352 (4)
O6^i—Co1—O7^ii	120.83 (9)	C18—C19—H19	126.7
O6^i—Co1—N1	90.41 (9)	N5—C19—H19	126.7
O7^ii—Co1—N1	85.73 (8)	C21—C20—C22	119.8 (3)
O6^i—Co1—N6	98.31 (9)	C21—C20—N5	119.3 (3)
O7^ii—Co1—N6	86.28 (8)	C22—C20—N5	120.8 (3)
N1—Co1—N6	170.37 (8)	C20—C21—C24	119.8 (3)
O6^i—Co1—O2	85.36 (8)	C20—C21—H21	120.1
O7^ii—Co1—O2	153.09 (8)	C24—C21—H21	120.1
N1—Co1—O2	101.30 (9)	C20—C22—C23	120.2 (3)
N6—Co1—O2	83.58 (9)	C20—C22—H22	119.9
O6^i—Co1—O1	140.87 (8)	C23—C22—H22	119.9
O7^ii—Co1—O1	97.98 (8)	C25—C23—C22	120.0 (3)
N1—Co1—O1	87.46 (8)	C25—C23—H23	120.0
N6—Co1—O1	88.34 (8)	C22—C23—H23	120.0
O2—Co1—O1	56.95 (7)	C25—C24—C21	120.5 (3)
O8^ii—Co2—O1	96.18 (9)	C25—C24—H24	119.7
O8^ii—Co2—O4^iii	93.14 (8)	C21—C24—H24	119.7
O1—Co2—O4^iii	85.75 (8)	C23—C25—C24	119.6 (3)
O8^ii—Co2—N3^iv	106.81 (9)	C23—C25—N4	121.0 (2)
O1—Co2—N3^iv	92.18 (9)	C24—C25—N4	119.4 (3)
O4^iii—Co2—N3^iv	160.04 (9)	N3—C26—N4	111.7 (2)
O8^ii—Co2—O10	97.82 (10)	N3—C26—H26	124.1
O1—Co2—O10	162.70 (9)	N4—C26—H26	124.1
O4^iii—Co2—O10	83.39 (9)	C28—C27—N4	106.4 (2)
N3^iv—Co2—O10	93.45 (10)	C28—C27—H27	126.8
O3—C1—O4	124.5 (3)	N4—C27—H27	126.8
O3—C1—C2	119.0 (3)	C27—C28—N3	110.3 (2)
O4—C1—C2	116.5 (2)	C27—C28—H28	124.8
C4—C2—C3	119.1 (2)	N3—C28—H28	124.8
C4—C2—C1	119.2 (2)	C31—C29—N1	110.4 (3)
C3—C2—C1	121.7 (2)	C31—C29—H29	124.8
C2—C3—C7	121.9 (2)	N1—C29—H29	124.8
C2—C3—H3	119.1	N1—C30—N2	111.9 (2)
C7—C3—H3	119.1	N1—C30—H30	124.0
C2—C4—C5	120.2 (3)	N2—C30—H30	124.0
C2—C4—H4	119.9	C29—C31—N2	106.3 (3)
C5—C4—H4	119.9	C29—C31—H31	126.9
C4—C5—C8	120.1 (3)	N2—C31—H31	126.9
C4—C5—H5	120.0	C34—C32—C33	118.8 (3)
C8—C5—H5	120.0	C34—C32—N2	120.6 (3)
O2—C6—O1	119.1 (2)	C33—C32—N2	120.6 (2)
O2—C6—C7	118.2 (2)	C32—C33—C34^v	121.2 (3)
O1—C6—C7	122.6 (2)	C32—C33—H33	119.4
C8—C7—C3	117.3 (2)	C34^v—C33—H33	119.4
C8—C7—C6	123.5 (2)	C32—C34—C33^v	120.0 (3)
C3—C7—C6	119.2 (2)	C32—C34—H34	120.0
C7—C8—C5	121.5 (2)	C33^v—C34—H34	120.0
C7—C8—O5	118.8 (2)	C30—N1—C29	105.1 (2)
C5—C8—O5	119.7 (2)	C30—N1—Co1	125.32 (18)
C10—C9—C11	120.5 (2)	C29—N1—Co1	129.30 (19)
C10—C9—O5	119.8 (2)	C30—N2—C31	106.2 (2)
C11—C9—O5	119.7 (2)	C30—N2—C32	127.6 (2)
C9—C10—C12	118.5 (3)	C31—N2—C32	125.9 (2)
C9—C10—H10	120.8	C26—N3—C28	104.9 (2)
C12—C10—H10	120.8	C26—N3—Co2^vi	130.5 (2)
C9—C11—C15	121.0 (2)	C28—N3—Co2^vi	124.12 (17)
C9—C11—H11	119.5	C26—N4—C27	106.7 (2)
C15—C11—H11	119.5	C26—N4—C25	127.8 (2)
C13—C12—C10	121.9 (2)	C27—N4—C25	125.4 (2)
C13—C12—H12	119.0	C17—N5—C19	106.4 (2)
C10—C12—H12	119.0	C17—N5—C20	126.8 (2)
C12—C13—C15	118.3 (2)	C19—N5—C20	126.6 (2)
C12—C13—C14	117.2 (2)	C17—N6—C18	105.2 (2)
C15—C13—C14	124.4 (2)	C17—N6—Co1	128.8 (2)
O9—C14—O8	126.5 (3)	C18—N6—Co1	125.84 (18)
O9—C14—C13	118.5 (2)	C6—O1—Co2	135.50 (18)
O8—C14—C13	114.8 (2)	C6—O1—Co1	87.77 (15)
C11—C15—C13	119.5 (2)	Co2—O1—Co1	134.61 (9)
C11—C15—C16	118.4 (2)	C6—O2—Co1	94.86 (16)
C13—C15—C16	122.0 (2)	C1—O4—Co2^iii	134.14 (18)
O6—C16—O7	126.0 (2)	C8—O5—C9	113.13 (19)
O6—C16—C15	115.8 (2)	C16—O6—Co1^i	147.55 (19)
O7—C16—C15	118.1 (2)	C16—O7—Co1^vii	125.94 (16)
N6—C17—N5	111.9 (3)	C14—O8—Co2^vii	138.55 (19)
N6—C17—H17	124.0	Co2—O10—H10A	139.9
N5—C17—H17	124.0	Co2—O10—H10B	106.0
C19—C18—N6	109.9 (2)	H10A—O10—H10B	107.9
C19—C18—H18	125.1	H11A—O11—H11B	111.4
N6—C18—H18	125.1	H12A—O12—H12B	107.7
C18—C19—N5	106.5 (3)	H13A—O13—H13B	105.6
O3—C1—C2—C4	−167.3 (3)	C33—C32—C34—C33^v	−0.6 (7)
O4—C1—C2—C4	12.3 (4)	N2—C32—C34—C33^v	178.8 (3)
O3—C1—C2—C3	15.1 (4)	N2—C30—N1—C29	0.3 (3)
O4—C1—C2—C3	−165.3 (2)	N2—C30—N1—Co1	175.15 (17)
C4—C2—C3—C7	−1.5 (4)	C31—C29—N1—C30	0.2 (4)
C1—C2—C3—C7	176.1 (2)	C31—C29—N1—Co1	−174.3 (2)
C3—C2—C4—C5	−0.5 (4)	N1—C30—N2—C31	−0.7 (3)
C1—C2—C4—C5	−178.2 (2)	N1—C30—N2—C32	−175.8 (3)
C2—C4—C5—C8	1.8 (4)	C29—C31—N2—C30	0.8 (4)
C2—C3—C7—C8	2.2 (4)	C29—C31—N2—C32	176.0 (3)
C2—C3—C7—C6	−177.5 (2)	C34—C32—N2—C30	−0.6 (5)
O2—C6—C7—C8	144.6 (3)	C33—C32—N2—C30	178.7 (3)
O1—C6—C7—C8	−38.5 (4)	C34—C32—N2—C31	−174.8 (3)
O2—C6—C7—C3	−35.7 (3)	C33—C32—N2—C31	4.6 (5)
O1—C6—C7—C3	141.1 (3)	N4—C26—N3—C28	0.1 (3)
C3—C7—C8—C5	−0.8 (4)	N4—C26—N3—Co2^vi	172.18 (19)
C6—C7—C8—C5	178.8 (2)	C27—C28—N3—C26	−0.1 (3)
C3—C7—C8—O5	−179.2 (2)	C27—C28—N3—Co2^vi	−172.8 (2)
C6—C7—C8—O5	0.5 (4)	N3—C26—N4—C27	−0.1 (3)
C4—C5—C8—C7	−1.1 (4)	N3—C26—N4—C25	176.7 (3)
C4—C5—C8—O5	177.2 (2)	C28—C27—N4—C26	0.0 (3)
C11—C9—C10—C12	−3.9 (4)	C28—C27—N4—C25	−176.9 (3)
O5—C9—C10—C12	176.4 (3)	C23—C25—N4—C26	−16.8 (5)
C10—C9—C11—C15	4.5 (4)	C24—C25—N4—C26	163.6 (3)
O5—C9—C11—C15	−175.7 (2)	C23—C25—N4—C27	159.5 (3)
C9—C10—C12—C13	−0.4 (5)	C24—C25—N4—C27	−20.2 (5)
C10—C12—C13—C15	4.0 (4)	N6—C17—N5—C19	0.9 (4)
C10—C12—C13—C14	−173.0 (3)	N6—C17—N5—C20	−173.4 (3)
C12—C13—C14—O9	−88.1 (3)	C18—C19—N5—C17	−1.9 (3)
C15—C13—C14—O9	95.1 (3)	C18—C19—N5—C20	172.3 (3)
C12—C13—C14—O8	86.9 (3)	C21—C20—N5—C17	24.2 (5)
C15—C13—C14—O8	−89.9 (3)	C22—C20—N5—C17	−158.7 (3)
C9—C11—C15—C13	−0.8 (4)	C21—C20—N5—C19	−149.0 (4)
C9—C11—C15—C16	175.8 (2)	C22—C20—N5—C19	28.2 (5)
C12—C13—C15—C11	−3.4 (4)	N5—C17—N6—C18	0.6 (3)
C14—C13—C15—C11	173.4 (3)	N5—C17—N6—Co1	−175.52 (19)
C12—C13—C15—C16	−179.9 (3)	C19—C18—N6—C17	−1.8 (3)
C14—C13—C15—C16	−3.1 (4)	C19—C18—N6—Co1	174.4 (2)
C11—C15—C16—O6	5.0 (4)	O2—C6—O1—Co2	175.42 (18)
C13—C15—C16—O6	−178.5 (2)	C7—C6—O1—Co2	−1.4 (4)
C11—C15—C16—O7	−172.7 (2)	O2—C6—O1—Co1	11.0 (2)
C13—C15—C16—O7	3.8 (4)	C7—C6—O1—Co1	−165.8 (2)
N6—C18—C19—N5	2.4 (3)	O1—C6—O2—Co1	−11.7 (3)
C22—C20—C21—C24	2.3 (6)	C7—C6—O2—Co1	165.20 (19)
N5—C20—C21—C24	179.5 (4)	O3—C1—O4—Co2^iii	−26.4 (4)
C21—C20—C22—C23	−2.2 (6)	C2—C1—O4—Co2^iii	154.07 (18)
N5—C20—C22—C23	−179.4 (3)	C7—C8—O5—C9	−128.1 (2)
C20—C22—C23—C25	0.0 (5)	C5—C8—O5—C9	53.6 (3)
C20—C21—C24—C25	−0.2 (7)	C10—C9—O5—C8	−122.9 (3)
C22—C23—C25—C24	2.1 (5)	C11—C9—O5—C8	57.3 (3)
C22—C23—C25—N4	−177.5 (3)	O7—C16—O6—Co1^i	−9.6 (6)
C21—C24—C25—C23	−2.0 (6)	C15—C16—O6—Co1^i	172.8 (2)
C21—C24—C25—N4	177.6 (4)	O6—C16—O7—Co1^vii	−41.7 (4)
N4—C27—C28—N3	0.0 (3)	C15—C16—O7—Co1^vii	135.8 (2)
N1—C29—C31—N2	−0.7 (4)	O9—C14—O8—Co2^vii	−23.3 (4)
C34—C32—C33—C34^v	0.6 (7)	C13—C14—O8—Co2^vii	162.15 (19)
N2—C32—C33—C34^v	−178.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O11^viii	0.95	2.53	3.319 (4)	140
C18—H18···O8^ii	0.95	2.65	3.523 (4)	153
C21—H21···O12^viii	0.95	2.54	3.294 (5)	136
C27—H27···O11^ix	0.95	2.51	3.314 (4)	142
C30—H30···O9^ii	0.95	2.58	3.485 (4)	160
C33—H33···O3^i	0.95	2.55	3.466 (4)	163
O10—H10A···O9^x	0.82	1.89	2.696 (3)	168
O10—H10B···O3^iii	0.83	1.90	2.697 (3)	160
O11—H11A···O12	0.87	1.89	2.733 (6)	164
O11—H11B···O2^viii	1.00	2.08	3.061 (4)	167
O12—H12A···O13^xi	0.83	1.98	2.801 (6)	172
O12—H12B···O3^viii	0.83	1.96	2.771 (4)	166
O13—H13A···O9^ii	0.84	1.97	2.804 (4)	173
O13—H13B···O11^xii	0.82	2.09	2.846 (6)	152

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1, y, z; (iii) −x, −y+1, −z+1; (viii) −x+1, −y+1, −z+1; (ix) x, y+1, z+1; (x) −x−1, −y+1, −z; (xi) −x+1, −y+1, −z; (xii) x, y+1, z.