Synthesis and crystal structure of a two-dimensional CoII coordination polymer: poly[(μ3-3-carb-oxy-benzoato)[μ2-5-(pyridin-4-yl)-1H,2'H-3,3'-bi[1,2,4-triazole]]cobalt(II)].

In the title compound, [Co(C8H5O4)(C9H6N7)] n , the divalent CoII atom is six-coordinated to three N atoms from two symmetrical 5-(pyridin-4-yl)-1H,2'H-3,3'-bi[1,2,4-triazole] (H2pyttz) ligands and three O atoms from three symmetrical 3-carb-oxy-benzoate (Hbdic) ligands, leading to a distorted {CoN3O3} octa-hedral coordination environment. Two CoII cations are linked by four bridging carboxyl-ate groups to generate a dinuclear [Co2(CO2)4] unit. The dinuclear units are further connected into a chain along [010] via the Hbdic ligands. The other infinite chain, along [100], is formed through the H2pyttz ligands. Finally, the two kinds of chains are cross-linked, by sharing the CoII cations, into a two-dimensional network. In the crystal, adjacent layers are further linked by O-H⋯N hydrogen bonds into a three-dimensional framework.

Chemical context

In recent years, the design and synthesis of coordination polymers (CPs) or metal–organic frameworks (MOFs) have attracted great inter­est because of their fascinating architectures and potential applications in areas such as gas storage and separation, catalysis, fluorescence, magnetism, mol­ecular recognition, conductivity etc (Kitagawa et al., 2004 ▸; Zhou et al., 2012 ▸; Cavka et al., 2014 ▸; Zhang et al., 2014 ▸; Huang et al., 2017 ▸; Nath et al., 2016 ▸; Ni et al., 2017 ▸; Yi et al., 2016 ▸; Sun et al., 2016 ▸). It is well known that organic ligands play a crucial role in the rational design and synthesis of coordination polymers (Li & Sato, 2017 ▸; Sun & Sun, 2015 ▸). Among the many organo­nitro­gen ligands, the rigid 5-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole) ligand (H2pyttz) attracted our attention for the following reasons. First, the H2pyttz ligand possesses seven potential N-donor coordination sites and can exhibit various coordination modes. Second, the uncoordinated N atoms are helpful for the construction of hydrogen bonds. The hydrogen bonds not only increase the diversity of coordination polymer structures, but also enhance their stability. With an increasing inter­est in H2pyttz organometallic systems, we report herein on the synthesis and crystal structure of the title compound [Co(C8H5O4)(C9H6N7)], (I).

Structural commentary

The asymmetric unit of (I) contains one independent CoII cation, one partially deprotonated Hpyttz− ligand and one partial deprotonated Hbtc− ligand. Notably, the deprotonated Hbtc− ligand adopts two different coordination modes. The deprotonated carboxyl­ate group has a bis­(monodentate) coordination mode to bridge two CoII centers while the undeprotonated carb­oxy­lic group adopts a monodentate mode. As shown in Fig. 1 ▸, the CoII cation is six-coordinated to three carb­oxy­lic oxygen atoms from three symmetrical Hbtc− ligands and three nitro­gen atoms from two symmetrical Hpyttz− ligands in a distorted [CoN3O3] octa­hedral coordination geometry. Four bridging carboxyl­ate groups link two CoII cations to generate a dinuclear [Co2(CO2)4] unit, which is further connected into an infinite chain along the b-axis direction. There exist eight- and 16-membered metallamacrocycles in the chain structure. In the 16-membered metallamacrocycle, the dihedral angle between the two aromatic rings is 0°, indicating the parallel orientation of the two aromatic rings.

Figure 1

Coordination environment of the CoII cation in (I) showing the atomic numbering scheme, with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (A) 1 − x, −y, 1 − z; (B) 1 − x, 1 − y, 1 − z; (C) −1 + x, y, z.]

The other infinite linear chain is along the a-axis direction with a Co⋯Co distance of 6.5825 (5) Å and Co—Co—Co angle of 180.00° and it is also generated through the coordination between the Hpyttz− ligands and the CoII cations. In the complex, the Hpyttz− ligand is almost coplanar, with dihedral angles of 7.48 (4), 6.87 (4) and 4.43 (4) ° between the pyridine and the two triazole rings, respectively. Finally, these two kinds of chains are cross-linked, by sharing the CoII cations, into a two-dimensional network.

Supra­molecular features

In the crystal, adjacent two-dimensional networks are packed parallel to each other in an ⋯AAAA⋯ fashion (Fig. 2 ▸). It should be noted that the carb­oxy­lic oxygen atom O3 and the uncoordinated nitro­gen atom N7 in adjacent networks inter­act with each other and form strong O3—H3⋯N7 hydrogen bonds (Table 1 ▸), which further link the two-dimensional networks into a three-dimensional supra­molecular architecture.

Figure 2

The three-dimensional structure of the title complex formed by the O—H⋯N hydrogen bonds (dashed lines) between adjacent networks (depicted in different colours). H atoms not involved in hydrogen bonds have been omitted for clarity.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N7i	0.89 (5)	1.72 (5)	2.592 (4)	166 (5)

Symmetry code: (i) .

Database survey

A search of the Cambridge Structural Database (Version 5.37; Groom et al., 2016 ▸) for 5-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole) reveals five structures. Of these, there is only one CoII coordination structure (ZOTDIX; Gong et al., 2014 ▸). In this structure, the pyridyl nitro­gen atom is not coordinated to the CoII cation.

Synthesis and crystallization

A mixture of Co(NO3)2 .6H2O (0.10 mmol), 5-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole) (0.10 mmol), benzene-1,3-di­carb­oxy­lic acid (0.10 mmol) and H2O (10 ml) was stirred at room temperature for 30 min. When the pH value had been adjusted to about 7.0 with 0.1 M NaOH, the mixture was sealed in a 20 ml Tefon-lined stainless-steel reactor and then heated to 433 K for 72 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 5 K h−1. Pink block-shaped crystals of the title complex were isolated, washed with distilled water, and dried in air (yield 52%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms attached to C and N atoms were placed in calculated positions (C—H = 0.93 Å, N—H = 0.86 Å) and refined as riding atoms with U iso(H) = 1.2U eq(C,N), respectively. The carboxyl H atom was located in the difference Fourier-map and refined isotropically with U iso(H) = 1.5U eq(O).

Table 2

Experimental details

Crystal data
Chemical formula	[Co(C8H5O4)(C9H6N7)]
M r	436.26
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c (Å)	6.5825 (5), 9.0574 (12), 13.9842 (12)
α, β, γ (°)	74.214 (1), 84.690 (2), 82.303 (1)
V (Å3)	793.69 (14)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.13
Crystal size (mm)	0.20 × 0.18 × 0.15
Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 ▸)
T min, T max	0.797, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	5565, 3507, 2338
R int	0.055
(sin θ/λ)max (Å−1)	0.669
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.061, 0.113, 1.09
No. of reflections	3507
No. of parameters	265
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.49, −0.59

Computer programs: SMART and SAINT (Bruker, 2008 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), SHELXTL (Sheldrick, 2008 ▸) and DIAMOND (Brandenburg & Putz, 2006 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901701533X/kq2016sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901701533X/kq2016Isup2.hkl

CCDC reference: 1498228

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

[Co(C8H5O4)(C9H6N7)]	Z = 2
Mr = 436.26	F(000) = 442
Triclinic, P1	Dx = 1.825 Mg m−3
a = 6.5825 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0574 (12) Å	Cell parameters from 1163 reflections
c = 13.9842 (12) Å	θ = 3.0–28.3°
α = 74.214 (1)°	µ = 1.13 mm−1
β = 84.690 (2)°	T = 293 K
γ = 82.303 (1)°	Block, pink
V = 793.69 (14) Å3	0.20 × 0.18 × 0.15 mm

Bruker SMART CCD area detector diffractometer	2338 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
φ and ω scans	θmax = 28.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
Tmin = 0.797, Tmax = 0.858	k = −11→12
5565 measured reflections	l = −16→18
3507 independent reflections

Refinement on F2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061	Hydrogen site location: mixed
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0172P)2 + 0.0319P] where P = (Fo2 + 2Fc2)/3
3507 reflections	(Δ/σ)max < 0.001
265 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

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.

	x	y	z	Uiso*/Ueq
Co1	0.36855 (8)	0.42648 (8)	0.65379 (5)	0.02024 (18)
N1	0.2335 (5)	0.5770 (4)	0.8362 (3)	0.0196 (9)
N2	0.3746 (5)	0.5162 (4)	0.7767 (3)	0.0182 (9)
N3	0.5482 (5)	0.6182 (4)	0.8697 (3)	0.0210 (9)
N4	0.9301 (5)	0.5039 (4)	0.7413 (3)	0.0200 (9)
H4	0.9832	0.5434	0.7811	0.024*
N5	1.0369 (5)	0.4445 (4)	0.6689 (3)	0.0197 (9)
N6	0.7019 (5)	0.4259 (4)	0.6688 (3)	0.0191 (9)
N7	0.0562 (5)	0.8553 (5)	1.1093 (3)	0.0273 (10)
O1	0.3534 (4)	0.3140 (4)	0.5493 (2)	0.0209 (7)
O2	0.6377 (4)	0.3585 (4)	0.4500 (2)	0.0209 (7)
O3	0.8393 (5)	−0.0128 (4)	0.2340 (3)	0.0342 (10)
H3	0.917 (7)	−0.071 (6)	0.200 (4)	0.051*
O4	0.6280 (4)	−0.1888 (4)	0.2391 (2)	0.0257 (8)
C1	0.5576 (6)	0.5438 (5)	0.7995 (3)	0.0180 (10)
C2	0.3424 (6)	0.6368 (5)	0.8906 (3)	0.0199 (10)
C3	0.7332 (6)	0.4911 (5)	0.7405 (3)	0.0173 (10)
C4	0.8918 (6)	0.3997 (5)	0.6277 (3)	0.0206 (11)
H4A	0.9183	0.3542	0.5751	0.025*
C5	−0.0515 (6)	0.7829 (6)	1.0630 (4)	0.0280 (12)
H5	−0.1909	0.7793	1.0807	0.034*
C6	0.0347 (6)	0.7140 (6)	0.9909 (4)	0.0282 (12)
H6	−0.0461	0.6662	0.9598	0.034*
C7	0.2431 (6)	0.7154 (5)	0.9641 (3)	0.0209 (10)
C8	0.3536 (6)	0.7892 (6)	1.0130 (4)	0.0297 (12)
H8	0.4938	0.7923	0.9977	0.036*
C9	0.2573 (7)	0.8578 (6)	1.0842 (4)	0.0300 (13)
H9	0.3342	0.9075	1.1159	0.036*
C10	0.4755 (6)	0.2952 (5)	0.4773 (3)	0.0186 (10)
C11	0.6668 (6)	−0.0715 (6)	0.2607 (3)	0.0213 (10)
C12	0.4189 (6)	0.1867 (5)	0.4224 (3)	0.0173 (10)
C13	0.5649 (6)	0.1212 (5)	0.3625 (3)	0.0191 (10)
H13	0.6973	0.1499	0.3523	0.023*
C14	0.5117 (6)	0.0126 (5)	0.3179 (3)	0.0198 (10)
C15	0.3112 (6)	−0.0227 (5)	0.3286 (3)	0.0235 (11)
H15	0.2761	−0.0946	0.2982	0.028*
C16	0.1631 (6)	0.0470 (6)	0.3834 (4)	0.0285 (12)
H16	0.0276	0.0257	0.3880	0.034*
C17	0.2189 (6)	0.1497 (6)	0.4316 (3)	0.0239 (11)
H17	0.1206	0.1943	0.4706	0.029*

	U11	U22	U33	U12	U13	U23
Co1	0.0155 (3)	0.0282 (4)	0.0212 (4)	−0.0045 (3)	0.0037 (2)	−0.0142 (3)
N1	0.0152 (18)	0.027 (2)	0.019 (2)	−0.0025 (16)	0.0041 (15)	−0.0124 (19)
N2	0.0152 (17)	0.022 (2)	0.019 (2)	−0.0014 (16)	0.0029 (15)	−0.0101 (19)
N3	0.0155 (18)	0.028 (2)	0.023 (2)	−0.0047 (16)	0.0039 (15)	−0.0132 (19)
N4	0.0158 (18)	0.030 (2)	0.019 (2)	−0.0041 (16)	0.0025 (15)	−0.0150 (19)
N5	0.0120 (17)	0.024 (2)	0.025 (2)	−0.0028 (16)	0.0053 (15)	−0.0112 (19)
N6	0.0159 (17)	0.027 (2)	0.019 (2)	−0.0039 (16)	0.0009 (15)	−0.0129 (19)
N7	0.031 (2)	0.029 (3)	0.025 (2)	−0.0022 (19)	0.0044 (18)	−0.016 (2)
O1	0.0245 (16)	0.0234 (19)	0.0183 (18)	−0.0064 (14)	0.0066 (13)	−0.0120 (15)
O2	0.0201 (15)	0.0205 (18)	0.0247 (19)	−0.0065 (13)	0.0016 (13)	−0.0096 (16)
O3	0.0267 (18)	0.041 (2)	0.043 (2)	−0.0092 (17)	0.0161 (16)	−0.029 (2)
O4	0.0300 (17)	0.026 (2)	0.026 (2)	−0.0057 (15)	0.0039 (14)	−0.0147 (17)
C1	0.018 (2)	0.022 (3)	0.016 (2)	−0.0021 (19)	0.0014 (17)	−0.008 (2)
C2	0.019 (2)	0.025 (3)	0.018 (3)	−0.006 (2)	0.0003 (18)	−0.010 (2)
C3	0.015 (2)	0.020 (3)	0.018 (2)	−0.0010 (18)	0.0004 (17)	−0.008 (2)
C4	0.017 (2)	0.022 (3)	0.026 (3)	0.000 (2)	0.0024 (19)	−0.014 (2)
C5	0.020 (2)	0.038 (3)	0.027 (3)	−0.004 (2)	0.010 (2)	−0.015 (3)
C6	0.021 (2)	0.042 (3)	0.027 (3)	−0.003 (2)	0.006 (2)	−0.021 (3)
C7	0.025 (2)	0.023 (3)	0.017 (3)	0.001 (2)	0.0010 (19)	−0.011 (2)
C8	0.017 (2)	0.044 (3)	0.034 (3)	−0.004 (2)	0.003 (2)	−0.022 (3)
C9	0.031 (3)	0.037 (3)	0.032 (3)	−0.009 (2)	0.002 (2)	−0.024 (3)
C10	0.016 (2)	0.016 (3)	0.023 (3)	0.0015 (19)	0.0000 (18)	−0.004 (2)
C11	0.022 (2)	0.026 (3)	0.016 (3)	−0.001 (2)	−0.0006 (18)	−0.007 (2)
C12	0.019 (2)	0.023 (3)	0.013 (2)	−0.0060 (19)	0.0008 (17)	−0.010 (2)
C13	0.016 (2)	0.025 (3)	0.019 (3)	−0.0109 (19)	0.0068 (17)	−0.009 (2)
C14	0.025 (2)	0.019 (3)	0.017 (2)	−0.004 (2)	0.0040 (18)	−0.008 (2)
C15	0.024 (2)	0.026 (3)	0.026 (3)	−0.008 (2)	0.002 (2)	−0.016 (2)
C16	0.021 (2)	0.038 (3)	0.033 (3)	−0.007 (2)	0.003 (2)	−0.019 (3)
C17	0.025 (2)	0.027 (3)	0.022 (3)	0.002 (2)	0.0048 (19)	−0.013 (2)

Co1—O1	2.012 (3)	O4—C11	1.244 (5)
Co1—O2i	2.086 (3)	O4—Co1iii	2.262 (4)
Co1—N2	2.097 (3)	C1—C3	1.461 (5)
Co1—N5ii	2.162 (3)	C2—C7	1.463 (5)
Co1—N6	2.223 (3)	C4—H4A	0.9300
Co1—O4iii	2.262 (4)	C5—C6	1.368 (5)
N1—C2	1.347 (5)	C5—H5	0.9300
N1—N2	1.352 (4)	C6—C7	1.389 (6)
N2—C1	1.345 (5)	C6—H6	0.9300
N3—C1	1.327 (5)	C7—C8	1.384 (6)
N3—C2	1.357 (5)	C8—C9	1.377 (6)
N4—C3	1.318 (5)	C8—H8	0.9300
N4—N5	1.368 (4)	C9—H9	0.9300
N4—H4	0.8600	C10—C12	1.502 (5)
N5—C4	1.320 (5)	C11—C14	1.495 (5)
N5—Co1iv	2.162 (3)	C12—C17	1.387 (6)
N6—C3	1.338 (5)	C12—C13	1.395 (5)
N6—C4	1.345 (5)	C13—C14	1.394 (5)
N7—C5	1.339 (5)	C13—H13	0.9300
N7—C9	1.339 (5)	C14—C15	1.385 (5)
O1—C10	1.262 (5)	C15—C16	1.377 (5)
O2—C10	1.258 (5)	C15—H15	0.9300
O2—Co1i	2.086 (3)	C16—C17	1.391 (6)
O3—C11	1.299 (5)	C16—H16	0.9300
O3—H3	0.89 (5)	C17—H17	0.9300
O1—Co1—O2i	93.18 (12)	N5—C4—N6	113.9 (4)
O1—Co1—N2	172.28 (15)	N5—C4—H4A	123.1
O2i—Co1—N2	94.31 (13)	N6—C4—H4A	123.1
O1—Co1—N5ii	87.27 (12)	N7—C5—C6	122.8 (4)
O2i—Co1—N5ii	91.64 (13)	N7—C5—H5	118.6
N2—Co1—N5ii	90.64 (12)	C6—C5—H5	118.6
O1—Co1—N6	105.23 (11)	C5—C6—C7	119.9 (4)
O2i—Co1—N6	90.18 (13)	C5—C6—H6	120.1
N2—Co1—N6	76.64 (12)	C7—C6—H6	120.1
N5ii—Co1—N6	167.25 (12)	C8—C7—C6	116.9 (4)
O1—Co1—O4iii	84.32 (12)	C8—C7—C2	121.6 (4)
O2i—Co1—O4iii	177.47 (11)	C6—C7—C2	121.4 (4)
N2—Co1—O4iii	88.17 (13)	C9—C8—C7	120.4 (4)
N5ii—Co1—O4iii	87.82 (13)	C9—C8—H8	119.8
N6—Co1—O4iii	90.88 (13)	C7—C8—H8	119.8
C2—N1—N2	105.2 (3)	N7—C9—C8	122.0 (4)
C1—N2—N1	105.6 (3)	N7—C9—H9	119.0
C1—N2—Co1	117.7 (3)	C8—C9—H9	119.0
N1—N2—Co1	136.0 (2)	O2—C10—O1	125.2 (4)
C1—N3—C2	100.7 (3)	O2—C10—C12	119.0 (4)
C3—N4—N5	109.5 (3)	O1—C10—C12	115.8 (4)
C3—N4—H4	125.2	O4—C11—O3	123.0 (4)
N5—N4—H4	125.2	O4—C11—C14	121.0 (4)
C4—N5—N4	103.0 (3)	O3—C11—C14	116.1 (4)
C4—N5—Co1iv	135.8 (3)	C17—C12—C13	119.2 (4)
N4—N5—Co1iv	121.0 (2)	C17—C12—C10	119.8 (4)
C3—N6—C4	103.5 (3)	C13—C12—C10	121.0 (4)
C3—N6—Co1	111.1 (2)	C14—C13—C12	119.8 (4)
C4—N6—Co1	144.9 (3)	C14—C13—H13	120.1
C5—N7—C9	118.1 (4)	C12—C13—H13	120.1
C10—O1—Co1	132.1 (3)	C15—C14—C13	119.8 (4)
C10—O2—Co1i	120.5 (3)	C15—C14—C11	118.3 (4)
C11—O3—H3	108 (3)	C13—C14—C11	121.9 (4)
C11—O4—Co1iii	124.8 (3)	C16—C15—C14	120.9 (4)
N3—C1—N2	114.7 (3)	C16—C15—H15	119.5
N3—C1—C3	130.7 (4)	C14—C15—H15	119.5
N2—C1—C3	114.6 (3)	C15—C16—C17	119.1 (4)
N1—C2—N3	113.8 (3)	C15—C16—H16	120.5
N1—C2—C7	121.9 (4)	C17—C16—H16	120.5
N3—C2—C7	124.3 (4)	C12—C17—C16	121.1 (4)
N4—C3—N6	110.1 (3)	C12—C17—H17	119.5
N4—C3—C1	130.3 (4)	C16—C17—H17	119.5
N6—C3—C1	119.5 (3)
C2—N1—N2—C1	−0.1 (5)	N1—C2—C7—C8	−173.9 (5)
C2—N1—N2—Co1	−169.6 (4)	N3—C2—C7—C8	5.4 (8)
C3—N4—N5—C4	0.5 (5)	N1—C2—C7—C6	8.8 (7)
C3—N4—N5—Co1iv	−174.9 (3)	N3—C2—C7—C6	−171.9 (5)
C2—N3—C1—N2	−0.1 (5)	C6—C7—C8—C9	−0.4 (8)
C2—N3—C1—C3	177.7 (5)	C2—C7—C8—C9	−177.8 (5)
N1—N2—C1—N3	0.1 (5)	C5—N7—C9—C8	0.2 (8)
Co1—N2—C1—N3	171.9 (3)	C7—C8—C9—N7	0.5 (8)
N1—N2—C1—C3	−178.1 (4)	Co1i—O2—C10—O1	−88.9 (5)
Co1—N2—C1—C3	−6.3 (5)	Co1i—O2—C10—C12	91.8 (4)
N2—N1—C2—N3	0.0 (5)	Co1—O1—C10—O2	−6.3 (7)
N2—N1—C2—C7	179.3 (4)	Co1—O1—C10—C12	173.1 (3)
C1—N3—C2—N1	0.1 (5)	Co1iii—O4—C11—O3	104.3 (5)
C1—N3—C2—C7	−179.3 (5)	Co1iii—O4—C11—C14	−77.2 (5)
N5—N4—C3—N6	−0.6 (5)	O2—C10—C12—C17	−162.0 (4)
N5—N4—C3—C1	−176.6 (5)	O1—C10—C12—C17	18.6 (6)
C4—N6—C3—N4	0.4 (5)	O2—C10—C12—C13	18.4 (7)
Co1—N6—C3—N4	−173.6 (3)	O1—C10—C12—C13	−161.0 (4)
C4—N6—C3—C1	177.0 (4)	C17—C12—C13—C14	−4.1 (7)
Co1—N6—C3—C1	3.0 (5)	C10—C12—C13—C14	175.5 (4)
N3—C1—C3—N4	−0.2 (9)	C12—C13—C14—C15	3.9 (7)
N2—C1—C3—N4	177.7 (5)	C12—C13—C14—C11	−174.3 (4)
N3—C1—C3—N6	−175.9 (5)	O4—C11—C14—C15	−13.1 (7)
N2—C1—C3—N6	1.9 (6)	O3—C11—C14—C15	165.5 (4)
N4—N5—C4—N6	−0.2 (5)	O4—C11—C14—C13	165.1 (5)
Co1iv—N5—C4—N6	174.1 (3)	O3—C11—C14—C13	−16.3 (7)
C3—N6—C4—N5	−0.1 (5)	C13—C14—C15—C16	−0.6 (7)
Co1—N6—C4—N5	170.1 (4)	C11—C14—C15—C16	177.7 (4)
C9—N7—C5—C6	−0.9 (8)	C14—C15—C16—C17	−2.5 (7)
N7—C5—C6—C7	1.0 (8)	C13—C12—C17—C16	1.0 (7)
C5—C6—C7—C8	−0.3 (7)	C10—C12—C17—C16	−178.6 (5)
C5—C6—C7—C2	177.1 (5)	C15—C16—C17—C12	2.3 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N7v	0.89 (5)	1.72 (5)	2.592 (4)	166 (5)