Hydroxonium creatininium bis­(pyridine-2,6-dicarboxyl­ato-κ³ O ²,N,O ⁶)cobaltate(II) trihydrate

Abstract

The title compound, (C₄H₈N₃O)(H₃O)[Co(C₇H₃NO₄)₂]·3H₂O, contains a protonated creatininium cation, a hydrox­onium (H₃O)⁺ cation, a [Co(pydc)₂]²⁻ (pydcH₂ = pyridine-2,6-dicarboxylic acid) complex anion, and three uncoordinated water mol­ecules. The Co^II atom is coordinated by four O and two N atoms from two pydc ligands in a distorted octa­hedral environment. The structure also contains three uncoordinated water mol­ecules. Extensive inter­molecular O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, π–π stacking inter­actions [centroid–centroid distances = 3.565 (14) and 3.425 (14) Å] and O⋯π inter­actions [O⋯centroid distance = 3.480 (2) Å] connect the various components in the crystal structure.

Related literature

For related structures, see: Aghabozorg, Derikvand et al. (2008 ▶); Aghabozorg, Ramezanipour et al. (2008 ▶); Moghimi et al. (2004 ▶, 2005 ▶). For a review article on proton-transfer agents and their metal complexes, see: Aghabozorg, Manteghi et al. (2008 ▶). For the isotypic Ni compound, see: Attar Gharamaleki et al. (2009 ▶).

Experimental

Crystal data

• (C₄H₈N₃O)(H₃O)[Co(C₇H₃NO₄)₂]·3H₂O

• M _r = 576.34

• Triclinic,

• a = 8.0937 (10) Å

• b = 10.7389 (13) Å

• c = 13.5976 (17) Å

• α = 104.811 (2)°

• β = 90.267 (2)°

• γ = 92.415 (1)°

• V = 1141.4 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 0.83 mm⁻¹

• T = 120 K

• 0.18 × 0.12 × 0.09 mm

Data collection

• Bruker SMART 1000 CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.889, T _max = 0.930

• 11652 measured reflections

• 5488 independent reflections

• 4149 reflections with I > 2σ(I)

• R _int = 0.025

Refinement

• R[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 0.097

• S = 1.02

• 5488 reflections

• 335 parameters

• H-atom parameters constrained

• Δρ_max = 0.77 e Å⁻³

• Δρ_min = −0.45 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Co1—N1	2.029 (2)
Co1—N2	2.031 (2)
Co1—O8	2.1273 (18)
Co1—O4	2.1389 (18)
Co1—O5	2.1904 (18)
Co1—O1	2.2239 (19)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1Wi	0.88	1.86	2.716 (3)	164
N5—H5A⋯O5	0.88	2.15	2.882 (3)	141
N5—H5B⋯O3ii	0.88	1.96	2.764 (3)	152
O1W—H1⋯O4iii	0.85	1.95	2.782 (3)	166
O1W—H2⋯O3Wiv	0.85	1.85	2.673 (3)	164
O2W—H3⋯O4Wv	0.85	1.70	2.522 (3)	163
O2W—H4⋯O6vi	0.85	1.64	2.481 (3)	170
O2W—H5⋯O2	0.85	1.71	2.537 (3)	164
O3W—H6⋯O7iii	0.85	1.93	2.778 (3)	172
O3W—H7⋯O9vii	0.85	2.22	2.948 (3)	144
O4W—H8⋯O7viii	0.85	1.84	2.680 (3)	169
O4W—H9⋯O1	0.85	1.87	2.718 (3)	172
C3—H3B⋯O9vii	0.95	2.37	3.301 (3)	165
C4—H4A⋯O8ix	0.95	2.43	3.252 (3)	145
C18—H18C⋯O7iii	0.98	2.60	3.535 (4)	160

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

supplementary crystallographic information

Comment

We have previously reported some compounds containing creatinine (creat), pyridine-2,6-dicarboxylic acid (pydcH₂) and various metals, such as (creatH)(pydcH).H₂O (Moghimi et al., 2004), (creatH)₂[Bi(pydc)₂]₂.4H₂O (Moghimi et al., 2005), (creatH)[Zn(pydc)(pydcH)].4H₂O (Aghabozorg, Ramezanipour et al., 2008) and (creatH)[Cr(pydc)₂](pydcH₂).6H₂O (Aghabozorg, Derikvand et al., 2008). For more details and related literature see our recent review article (Aghabozorg, Manteghi et al., 2008).

We describe here the crystal structure of the title compound. The compound contains a [Co(pydc)₂]^2- anion, a (creatH)⁺ and a (H₃O)⁺ cation, and three uncoordinated water molecules (Fig. 1). In the anion, the Co^II atom is six-coordinated by two N atoms (N1 and N2) and four O atoms (O1, O4, O5 and O8) from the carboxylate groups of two (pydc)^2- ligands, with the bond length range of 2.029 (2)–2.2239 (19) Å (Table 1). The N1—Co1—N2 [171.90 (8)°], O8—Co1—O5 [151.26 (7)°] and O4—Co1—O1 [152.09 (7)°] angles show that the four carboxylate groups of the two (pydc)^2- ligands orient in a flattened tetrahedral arrangement around the central atom. The coordination environment around Co^II is distorted octahedral. The O8—Co1—O4—C7 and O1—Co1—O8—C14 torsion angles are -95.15 (17)° and 95.48 (19)°, respectively, thus it can be concluded that two (pydc)^2- ligands are almost perpendicular to each other. The intermolecular forces in the structure could be divided in three main branches, ionic interactions which gather principal anionic complex and counter cation together, X—H···O hydrogen bonds (Fig. 2 and Table 2), where X= O, N, C, and O···π, π–π stacking interactions. The π–π stacking interactions between the pyridyl rings, with centroid–centroid distances of 3.565 (14) and 3.425 (14) Å, and the O···π interaction between the carboxylate O atom and pyridyl ring, with an O···centroid distance of 3.480 (2)Å are observed (Fig. 3). Ion pairing, π–π stacking interactions and extensive intermolecular hydrogen bonds connected the various components into a supramolecular structure.

Experimental

The reaction between pyridine-2,6-dicarboxylic acid (100 mg, 1 mmol) in 10 ml water, cratinine (110 mg, 1 mmol) in 20 ml water and Co(NO₃)₂.6H₂O (87 mg, 0.5 mmol) in 5 ml water at a 2:2:1 molar ratio gave a red compound after slow evaporation of the solvent at the room temperature. The crystals obtained were stable in air.

Refinement

H atoms on O and N atoms were found from difference Fourier maps. H atoms on C atoms were positioned geometrically. All H atoms were refined in riding models, with U_iso(H) = 1.2(1.5 for methyl)U_eq(C,N) or 1.5U_eq(O).

Figures

Fig. 1.

Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

Packing diagram of the title compound. Hydrogen bonds are shown by dashed lines.

Fig. 3.

The π–π and O···π stacking interactions in the title compound. The centroid–centroid distances are 3.425 (14) Å between Cg1 (N1, C2–C6) and Cg1i, and 3.565 (14) Å between Cg2ii (N2ii, C9ii–C13ii) and Cg2iii. The O7···Cg2iii distance is 3.480 (2) Å. [Symmetry codes: (i) 1-x, 2-y, 1-z; (ii) 1+x, y, z; (iii) 1-x, 2-y, -z.]

Crystal data

(C4H8N3O)(H3O)[Co(C7H3NO4)2]·3H2O	Z = 2
Mr = 576.34	F(000) = 594
Triclinic, P1	Dx = 1.677 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0937 (10) Å	Cell parameters from 843 reflections
b = 10.7389 (13) Å	θ = 3–27°
c = 13.5976 (17) Å	µ = 0.83 mm−1
α = 104.811 (2)°	T = 120 K
β = 90.267 (2)°	Prism, red
γ = 92.415 (1)°	0.18 × 0.12 × 0.09 mm
V = 1141.4 (2) Å3

Data collection

Bruker SMART 1000 CCD diffractometer	5488 independent reflections
Radiation source: fine-focus sealed tube	4149 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 28.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.889, Tmax = 0.930	k = −14→14
11652 measured reflections	l = −17→17

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)] = 0.045	Hydrogen site location: mixed
wR(F2) = 0.097	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.015P)2 + 2.6P] where P = (Fo2 + 2Fc2)/3
5488 reflections	(Δ/σ)max < 0.001
335 parameters	Δρmax = 0.77 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

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

	x	y	z	Uiso*/Ueq
Co1	0.26506 (4)	0.93000 (3)	0.23131 (3)	0.01942 (10)
O1	0.4562 (2)	0.78341 (18)	0.19033 (13)	0.0230 (4)
O2	0.6104 (2)	0.65616 (18)	0.25814 (14)	0.0252 (4)
O3	0.0940 (2)	1.13617 (18)	0.50661 (14)	0.0254 (4)
O4	0.1083 (2)	1.04931 (18)	0.33852 (13)	0.0232 (4)
O5	0.0722 (2)	0.78287 (17)	0.16490 (13)	0.0220 (4)
O6	−0.0601 (2)	0.69039 (18)	0.01715 (13)	0.0249 (4)
O7	0.4810 (2)	1.23340 (18)	0.13445 (13)	0.0238 (4)
O8	0.4131 (2)	1.09779 (18)	0.22942 (13)	0.0241 (4)
O9	0.2979 (2)	0.47606 (19)	0.53766 (14)	0.0287 (4)
N1	0.3283 (2)	0.89101 (19)	0.36453 (15)	0.0161 (4)
N2	0.2268 (2)	0.9517 (2)	0.08903 (15)	0.0170 (4)
N3	0.1336 (3)	0.5901 (2)	0.45644 (15)	0.0181 (4)
H3A	0.0801	0.6346	0.5091	0.022*
N4	0.2130 (3)	0.5206 (2)	0.29648 (16)	0.0202 (4)
N5	0.0027 (3)	0.6690 (2)	0.33142 (15)	0.0210 (5)
H5A	−0.0074	0.6703	0.2672	0.025*
H5B	−0.0602	0.7165	0.3776	0.025*
C1	0.5092 (3)	0.7418 (2)	0.26371 (18)	0.0188 (5)
C2	0.4403 (3)	0.8035 (2)	0.36658 (19)	0.0180 (5)
C3	0.4860 (3)	0.7762 (2)	0.45730 (19)	0.0198 (5)
H3B	0.5660	0.7143	0.4584	0.024*
C4	0.4112 (3)	0.8422 (2)	0.54679 (19)	0.0203 (5)
H4A	0.4382	0.8245	0.6098	0.024*
C5	0.2971 (3)	0.9341 (2)	0.54291 (19)	0.0206 (5)
H5C	0.2460	0.9807	0.6031	0.025*
C6	0.2589 (3)	0.9566 (2)	0.44902 (18)	0.0174 (5)
C7	0.1427 (3)	1.0555 (2)	0.43192 (19)	0.0190 (5)
C8	0.0403 (3)	0.7707 (2)	0.07148 (18)	0.0191 (5)
C9	0.1295 (3)	0.8660 (2)	0.02324 (18)	0.0177 (5)
C10	0.1127 (3)	0.8709 (3)	−0.07723 (19)	0.0201 (5)
H10A	0.0447	0.8087	−0.1240	0.024*
C11	0.1983 (3)	0.9690 (3)	−0.10736 (19)	0.0222 (5)
H11A	0.1896	0.9743	−0.1759	0.027*
C12	0.2966 (3)	1.0597 (3)	−0.03808 (19)	0.0200 (5)
H12A	0.3538	1.1283	−0.0578	0.024*
C13	0.3090 (3)	1.0472 (2)	0.06107 (19)	0.0180 (5)
C14	0.4103 (3)	1.1339 (2)	0.14799 (19)	0.0199 (5)
C15	0.1105 (3)	0.5968 (2)	0.35806 (18)	0.0182 (5)
C16	0.3147 (3)	0.4547 (3)	0.35453 (19)	0.0221 (5)
H16A	0.4336	0.4783	0.3505	0.027*
H16B	0.2976	0.3599	0.3303	0.027*
C17	0.2520 (3)	0.5040 (3)	0.4611 (2)	0.0213 (5)
C18	0.2037 (4)	0.4869 (3)	0.18563 (19)	0.0279 (6)
H18A	0.2195	0.5652	0.1617	0.042*
H18B	0.0951	0.4457	0.1627	0.042*
H18C	0.2903	0.4272	0.1580	0.042*
O1W	−0.0036 (2)	0.29618 (18)	0.36045 (14)	0.0249 (4)
H1	0.0162	0.2166	0.3476	0.037*
H2	−0.0856	0.3008	0.3225	0.037*
O2W	0.7786 (2)	0.55028 (19)	0.10484 (14)	0.0293 (4)
H3	0.7269	0.4912	0.0603	0.044*
H4	0.8232	0.6010	0.0728	0.044*
H5	0.7115	0.5907	0.1481	0.044*
O3W	0.7461 (3)	0.3583 (2)	0.25576 (16)	0.0362 (5)
H6	0.6588	0.3236	0.2235	0.054*
H7	0.7240	0.4284	0.2983	0.054*
O4W	0.3941 (3)	0.6406 (2)	−0.00313 (15)	0.0468 (7)
H8	0.4336	0.6891	−0.0386	0.070*
H9	0.4122	0.6782	0.0592	0.070*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.02341 (19)	0.02192 (19)	0.01396 (17)	0.00133 (14)	−0.00051 (13)	0.00646 (13)
O1	0.0280 (10)	0.0275 (10)	0.0147 (9)	0.0058 (8)	0.0015 (7)	0.0067 (7)
O2	0.0268 (10)	0.0296 (10)	0.0195 (9)	0.0106 (8)	0.0029 (8)	0.0051 (8)
O3	0.0299 (10)	0.0242 (10)	0.0208 (9)	0.0052 (8)	0.0040 (8)	0.0027 (8)
O4	0.0289 (10)	0.0246 (10)	0.0173 (9)	0.0063 (8)	0.0022 (7)	0.0065 (7)
O5	0.0269 (10)	0.0249 (10)	0.0152 (9)	−0.0037 (8)	−0.0011 (7)	0.0075 (7)
O6	0.0303 (10)	0.0264 (10)	0.0168 (9)	−0.0080 (8)	−0.0021 (8)	0.0048 (8)
O7	0.0279 (10)	0.0247 (10)	0.0197 (9)	−0.0077 (8)	−0.0030 (8)	0.0091 (8)
O8	0.0328 (10)	0.0253 (10)	0.0155 (9)	−0.0052 (8)	−0.0017 (8)	0.0086 (7)
O9	0.0327 (11)	0.0354 (11)	0.0201 (9)	0.0093 (9)	−0.0025 (8)	0.0100 (8)
N1	0.0173 (10)	0.0173 (10)	0.0136 (9)	−0.0022 (8)	0.0000 (8)	0.0042 (8)
N2	0.0173 (10)	0.0195 (11)	0.0142 (10)	0.0018 (8)	−0.0002 (8)	0.0043 (8)
N3	0.0199 (10)	0.0216 (11)	0.0133 (10)	0.0024 (8)	0.0011 (8)	0.0050 (8)
N4	0.0224 (11)	0.0230 (11)	0.0153 (10)	0.0054 (9)	−0.0002 (8)	0.0047 (9)
N5	0.0255 (11)	0.0262 (12)	0.0116 (10)	0.0025 (9)	0.0010 (8)	0.0051 (9)
C1	0.0199 (12)	0.0205 (13)	0.0150 (11)	−0.0018 (10)	−0.0008 (9)	0.0033 (10)
C2	0.0167 (12)	0.0184 (12)	0.0179 (12)	−0.0009 (9)	0.0010 (9)	0.0035 (10)
C3	0.0193 (12)	0.0214 (13)	0.0193 (12)	−0.0009 (10)	−0.0028 (10)	0.0067 (10)
C4	0.0242 (13)	0.0231 (13)	0.0141 (11)	−0.0049 (10)	−0.0038 (10)	0.0067 (10)
C5	0.0227 (13)	0.0231 (13)	0.0141 (12)	−0.0035 (10)	0.0020 (10)	0.0021 (10)
C6	0.0172 (12)	0.0178 (12)	0.0165 (12)	−0.0023 (9)	0.0003 (9)	0.0037 (10)
C7	0.0180 (12)	0.0178 (12)	0.0219 (12)	0.0009 (10)	0.0031 (10)	0.0062 (10)
C8	0.0210 (12)	0.0194 (12)	0.0166 (12)	0.0011 (10)	0.0013 (10)	0.0039 (10)
C9	0.0185 (12)	0.0175 (12)	0.0171 (12)	0.0023 (10)	0.0020 (9)	0.0042 (10)
C10	0.0187 (12)	0.0246 (13)	0.0155 (12)	0.0009 (10)	−0.0006 (9)	0.0028 (10)
C11	0.0250 (13)	0.0286 (14)	0.0143 (12)	0.0030 (11)	0.0002 (10)	0.0074 (10)
C12	0.0188 (12)	0.0238 (13)	0.0193 (12)	0.0036 (10)	0.0032 (10)	0.0087 (10)
C13	0.0160 (12)	0.0194 (12)	0.0201 (12)	0.0037 (9)	0.0018 (9)	0.0074 (10)
C14	0.0180 (12)	0.0239 (13)	0.0181 (12)	0.0014 (10)	0.0003 (10)	0.0059 (10)
C15	0.0194 (12)	0.0185 (12)	0.0158 (12)	−0.0035 (10)	0.0001 (9)	0.0031 (10)
C16	0.0225 (13)	0.0246 (13)	0.0195 (12)	0.0042 (11)	−0.0009 (10)	0.0056 (10)
C17	0.0197 (12)	0.0216 (13)	0.0227 (13)	0.0003 (10)	−0.0019 (10)	0.0062 (10)
C18	0.0381 (16)	0.0293 (15)	0.0149 (12)	0.0067 (12)	0.0010 (11)	0.0024 (11)
O1W	0.0284 (10)	0.0249 (10)	0.0216 (9)	0.0065 (8)	−0.0015 (8)	0.0052 (8)
O2W	0.0354 (11)	0.0256 (10)	0.0246 (10)	−0.0025 (9)	0.0084 (8)	0.0027 (8)
O3W	0.0351 (12)	0.0370 (12)	0.0304 (11)	0.0082 (10)	−0.0113 (9)	−0.0037 (9)
O4W	0.0845 (19)	0.0357 (13)	0.0170 (10)	−0.0282 (12)	0.0008 (11)	0.0061 (9)

Geometric parameters (Å, °)

Co1—N1	2.029 (2)	C3—H3B	0.9500
Co1—N2	2.031 (2)	C4—C5	1.390 (4)
Co1—O8	2.1273 (18)	C4—H4A	0.9500
Co1—O4	2.1389 (18)	C5—C6	1.394 (3)
Co1—O5	2.1904 (18)	C5—H5C	0.9500
Co1—O1	2.2239 (19)	C6—C7	1.509 (3)
O1—C1	1.273 (3)	C8—C9	1.511 (3)
O2—C1	1.245 (3)	C9—C10	1.387 (3)
O3—C7	1.233 (3)	C10—C11	1.386 (4)
O4—C7	1.283 (3)	C10—H10A	0.9500
O5—C8	1.268 (3)	C11—C12	1.388 (4)
O6—C8	1.249 (3)	C11—H11A	0.9500
O7—C14	1.247 (3)	C12—C13	1.392 (3)
O8—C14	1.263 (3)	C12—H12A	0.9500
O9—C17	1.215 (3)	C13—C14	1.516 (3)
N1—C6	1.325 (3)	C16—C17	1.509 (4)
N1—C2	1.338 (3)	C16—H16A	0.9900
N2—C9	1.334 (3)	C16—H16B	0.9900
N2—C13	1.335 (3)	C18—H18A	0.9800
N3—C15	1.370 (3)	C18—H18B	0.9800
N3—C17	1.371 (3)	C18—H18C	0.9800
N3—H3A	0.8800	O1W—H1	0.8500
N4—C15	1.331 (3)	O1W—H2	0.8500
N4—C18	1.458 (3)	O2W—H3	0.8500
N4—C16	1.459 (3)	O2W—H4	0.8500
N5—C15	1.301 (3)	O2W—H5	0.8500
N5—H5A	0.8800	O3W—H6	0.8500
N5—H5B	0.8800	O3W—H7	0.8500
C1—C2	1.507 (3)	O4W—H8	0.8500
C2—C3	1.391 (3)	O4W—H9	0.8500
C3—C4	1.397 (4)
N1—Co1—N2	171.90 (8)	N1—C6—C7	113.5 (2)
N1—Co1—O8	104.11 (7)	C5—C6—C7	125.5 (2)
N2—Co1—O8	76.44 (7)	O3—C7—O4	126.1 (2)
N1—Co1—O4	77.02 (8)	O3—C7—C6	118.5 (2)
N2—Co1—O4	111.08 (8)	O4—C7—C6	115.4 (2)
O8—Co1—O4	88.59 (7)	O6—C8—O5	126.3 (2)
N1—Co1—O5	104.55 (7)	O6—C8—C9	117.6 (2)
N2—Co1—O5	75.49 (7)	O5—C8—C9	116.1 (2)
O8—Co1—O5	151.26 (7)	N2—C9—C10	121.4 (2)
O4—Co1—O5	95.77 (7)	N2—C9—C8	112.8 (2)
N1—Co1—O1	75.10 (7)	C10—C9—C8	125.8 (2)
N2—Co1—O1	96.82 (7)	C11—C10—C9	118.0 (2)
O8—Co1—O1	99.21 (7)	C11—C10—H10A	121.0
O4—Co1—O1	152.09 (7)	C9—C10—H10A	121.0
O5—Co1—O1	90.12 (7)	C10—C11—C12	120.4 (2)
C1—O1—Co1	115.11 (16)	C10—C11—H11A	119.8
C7—O4—Co1	114.49 (16)	C12—C11—H11A	119.8
C8—O5—Co1	115.09 (16)	C11—C12—C13	118.1 (2)
C14—O8—Co1	116.51 (16)	C11—C12—H12A	121.0
C6—N1—C2	121.3 (2)	C13—C12—H12A	121.0
C6—N1—Co1	118.26 (17)	N2—C13—C12	120.9 (2)
C2—N1—Co1	120.43 (16)	N2—C13—C14	112.3 (2)
C9—N2—C13	121.1 (2)	C12—C13—C14	126.8 (2)
C9—N2—Co1	119.81 (16)	O7—C14—O8	125.7 (2)
C13—N2—Co1	118.89 (16)	O7—C14—C13	118.6 (2)
C15—N3—C17	110.3 (2)	O8—C14—C13	115.6 (2)
C15—N3—H3A	124.8	N5—C15—N4	126.3 (2)
C17—N3—H3A	124.8	N5—C15—N3	123.3 (2)
C15—N4—C18	125.2 (2)	N4—C15—N3	110.4 (2)
C15—N4—C16	110.1 (2)	N4—C16—C17	102.3 (2)
C18—N4—C16	123.7 (2)	N4—C16—H16A	111.3
C15—N5—H5A	120.0	C17—C16—H16A	111.3
C15—N5—H5B	120.0	N4—C16—H16B	111.3
H5A—N5—H5B	120.0	C17—C16—H16B	111.3
O2—C1—O1	126.4 (2)	H16A—C16—H16B	109.2
O2—C1—C2	118.0 (2)	O9—C17—N3	125.7 (2)
O1—C1—C2	115.6 (2)	O9—C17—C16	127.5 (2)
N1—C2—C3	121.2 (2)	N3—C17—C16	106.8 (2)
N1—C2—C1	113.7 (2)	N4—C18—H18A	109.5
C3—C2—C1	125.1 (2)	N4—C18—H18B	109.5
C2—C3—C4	118.3 (2)	H18A—C18—H18B	109.5
C2—C3—H3B	120.9	N4—C18—H18C	109.5
C4—C3—H3B	120.9	H18A—C18—H18C	109.5
C5—C4—C3	119.4 (2)	H18B—C18—H18C	109.5
C5—C4—H4A	120.3	H1—O1W—H2	105.5
C3—C4—H4A	120.3	H3—O2W—H4	106.0
C4—C5—C6	118.7 (2)	H3—O2W—H5	110.2
C4—C5—H5C	120.6	H4—O2W—H5	109.9
C6—C5—H5C	120.6	H6—O3W—H7	110.0
N1—C6—C5	121.0 (2)	H8—O4W—H9	108.1
N1—Co1—O1—C1	2.34 (17)	C2—N1—C6—C5	−1.7 (4)
N2—Co1—O1—C1	−178.09 (18)	Co1—N1—C6—C5	179.89 (18)
O8—Co1—O1—C1	104.61 (18)	C2—N1—C6—C7	177.0 (2)
O4—Co1—O1—C1	0.0 (3)	Co1—N1—C6—C7	−1.4 (3)
O5—Co1—O1—C1	−102.69 (18)	C4—C5—C6—N1	0.7 (4)
N1—Co1—O4—C7	9.68 (17)	C4—C5—C6—C7	−177.8 (2)
N2—Co1—O4—C7	−170.03 (17)	Co1—O4—C7—O3	164.3 (2)
O8—Co1—O4—C7	−95.15 (17)	Co1—O4—C7—C6	−13.2 (3)
O5—Co1—O4—C7	113.32 (17)	N1—C6—C7—O3	−167.8 (2)
O1—Co1—O4—C7	12.1 (3)	C5—C6—C7—O3	10.9 (4)
N1—Co1—O5—C8	−164.94 (17)	N1—C6—C7—O4	10.0 (3)
N2—Co1—O5—C8	6.69 (17)	C5—C6—C7—O4	−171.4 (2)
O8—Co1—O5—C8	19.4 (3)	Co1—O5—C8—O6	177.3 (2)
O4—Co1—O5—C8	117.01 (18)	Co1—O5—C8—C9	−4.7 (3)
O1—Co1—O5—C8	−90.32 (18)	C13—N2—C9—C10	1.5 (4)
N1—Co1—O8—C14	172.30 (18)	Co1—N2—C9—C10	−173.89 (18)
N2—Co1—O8—C14	0.63 (18)	C13—N2—C9—C8	−176.7 (2)
O4—Co1—O8—C14	−111.46 (19)	Co1—N2—C9—C8	7.9 (3)
O5—Co1—O8—C14	−12.0 (3)	O6—C8—C9—N2	176.6 (2)
O1—Co1—O8—C14	95.48 (19)	O5—C8—C9—N2	−1.6 (3)
O8—Co1—N1—C6	81.22 (18)	O6—C8—C9—C10	−1.5 (4)
O4—Co1—N1—C6	−3.96 (17)	O5—C8—C9—C10	−179.7 (2)
O5—Co1—N1—C6	−96.65 (18)	N2—C9—C10—C11	−1.1 (4)
O1—Co1—N1—C6	177.18 (19)	C8—C9—C10—C11	176.9 (2)
O8—Co1—N1—C2	−97.19 (19)	C9—C10—C11—C12	−0.4 (4)
O4—Co1—N1—C2	177.62 (19)	C10—C11—C12—C13	1.3 (4)
O5—Co1—N1—C2	84.94 (19)	C9—N2—C13—C12	−0.5 (4)
O1—Co1—N1—C2	−1.23 (17)	Co1—N2—C13—C12	174.95 (18)
O8—Co1—N2—C9	178.3 (2)	C9—N2—C13—C14	179.3 (2)
O4—Co1—N2—C9	−98.58 (19)	Co1—N2—C13—C14	−5.2 (3)
O5—Co1—N2—C9	−7.92 (18)	C11—C12—C13—N2	−0.9 (4)
O1—Co1—N2—C9	80.44 (19)	C11—C12—C13—C14	179.3 (2)
O8—Co1—N2—C13	2.82 (17)	Co1—O8—C14—O7	175.7 (2)
O4—Co1—N2—C13	85.92 (19)	Co1—O8—C14—C13	−3.5 (3)
O5—Co1—N2—C13	176.59 (19)	N2—C13—C14—O7	−173.6 (2)
O1—Co1—N2—C13	−95.06 (18)	C12—C13—C14—O7	6.2 (4)
Co1—O1—C1—O2	176.8 (2)	N2—C13—C14—O8	5.6 (3)
Co1—O1—C1—C2	−3.0 (3)	C12—C13—C14—O8	−174.6 (2)
C6—N1—C2—C3	1.2 (4)	C18—N4—C15—N5	−11.3 (4)
Co1—N1—C2—C3	179.52 (18)	C16—N4—C15—N5	−179.8 (2)
C6—N1—C2—C1	−178.2 (2)	C18—N4—C15—N3	168.9 (2)
Co1—N1—C2—C1	0.2 (3)	C16—N4—C15—N3	0.4 (3)
O2—C1—C2—N1	−177.8 (2)	C17—N3—C15—N5	178.5 (2)
O1—C1—C2—N1	2.0 (3)	C17—N3—C15—N4	−1.7 (3)
O2—C1—C2—C3	2.9 (4)	C15—N4—C16—C17	0.9 (3)
O1—C1—C2—C3	−177.4 (2)	C18—N4—C16—C17	−167.8 (2)
N1—C2—C3—C4	0.4 (4)	C15—N3—C17—O9	−179.0 (3)
C1—C2—C3—C4	179.6 (2)	C15—N3—C17—C16	2.2 (3)
C2—C3—C4—C5	−1.3 (4)	N4—C16—C17—O9	179.4 (3)
C3—C4—C5—C6	0.8 (4)	N4—C16—C17—N3	−1.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1Wi	0.88	1.86	2.716 (3)	164
N5—H5A···O5	0.88	2.15	2.882 (3)	141
N5—H5B···O3ii	0.88	1.96	2.764 (3)	152
O1W—H1···O4iii	0.85	1.95	2.782 (3)	166
O1W—H2···O3Wiv	0.85	1.85	2.673 (3)	164
O2W—H3···O4Wv	0.85	1.70	2.522 (3)	163
O2W—H4···O6vi	0.85	1.64	2.481 (3)	170
O2W—H5···O2	0.85	1.71	2.537 (3)	164
O3W—H6···O7iii	0.85	1.93	2.778 (3)	172
O3W—H7···O9vii	0.85	2.22	2.948 (3)	144
O4W—H8···O7viii	0.85	1.84	2.680 (3)	169
O4W—H9···O1	0.85	1.87	2.718 (3)	172
C3—H3B···O9vii	0.95	2.37	3.301 (3)	165
C4—H4A···O8ix	0.95	2.43	3.252 (3)	145
C18—H18C···O7iii	0.98	2.60	3.535 (4)	160

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