Bis[N5,N7-bis­(pyridin-2-yl)-6,7-di­hydro-5H-pyrrolo­[3,4-b]pyrazine-5,7-di­imine]­cobalt(III) perchlorate aceto­nitrile disolvate

Posel, M.; Stoeckli-Evans, H.

doi:10.1107/S241431461800754X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 5| May 2018| x180754

https://doi.org/10.1107/S241431461800754X

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Bis[N⁵,N⁷-bis(pyridin-2-yl)-6,7-dihydro-5H-pyrrolo[3,4-b]pyrazine-5,7-diimine]cobalt(III) perchlorate acetonitrile disolvate

Maciej Posel ^a and Helen Stoeckli-Evans ^b ^*

^aInstitute of Chemistry, University of Neuchâtel, Av de Bellevaux 51, CH-2000 Neuchâtel, Switzerland, and ^bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 2 May 2018; accepted 18 May 2018; online 25 May 2018)

In the title complex, [Co(C₁₆H₁₀N₇)₂]ClO₄·2CH₃CN, the cation possesses twofold rotational symmetry. The Co^III ion is located on a twofold rotation axis and is octahedrally coordinated to two tridentate `pincer' ligands. The Cl atom of the perchlorate anion is located on a fourfold rotoinversion axis. In the crystal, the cations are linked via C—H⋯O and C—H⋯N hydrogen bonds involving the perchlorate anion and the solvate acetonitrile molecules. These interactions lead to the formation of a supramolecular three-dimensional framework.

Keywords: crystal structure; pyrrolopyrazine; pincer ligand; isoindoline analogue; cobalt(III); hydrogen bonding; supramolecular framework.

CCDC reference: 1844111

Structure description

Symmetrically substituted isoindolines, such as 1,3-bis(2-pyridylinimo)isoindoline (Schilf, 2004 ), are ideal tridentate `pincer' ligands. For example, two isotypic cobalt(II) complexes of deprotonated 1,3-bis(2-pyridylinimo)isoindoline have been synthesized and their interaction with calf-thymus DNA studied (Selvi et al., 2005 ). The same ligand has been used to form a neutral square-planar platinum(II) complex that has a bright-orange to red room temperature luminescence in fluid dichloromethane solutions (Wen et al., 2010 ).

The pyrazine analogue of 1,3-bis(2-pyridylinimo)isoindoline, viz. (5Z,7Z)-N⁵,N⁷-di(pyridin-2-yl)-5H-pyrrolo[3,4-b]pyrazine-5,7(6H)-diimine (L) (Posel & Stoeckli-Evans, 2018 ), was synthesized in order to study its coordination behaviour with transition metals (Posel, 1998 ). Herein, we describe one such complex synthesized by the reaction of L with cobalt perchlorate.

The molecular structure of the title complex cation is illustrated in Fig. 1. It possesses twofold rotational symmetry with the cobalt atom located on a twofold rotation axis. It is ligated by six N atoms from two deprotonated tridentate L ligands, hence it has an almost perfect octahedral coordination sphere. The Co—N_imine bond length (Co1—N5) is 1.885 (5) Å, shorter than the Co—N_pyridine bond lengths (Co1—N4 and Co1—N7) of 1.983 (6) and 1.979 (5) Å. These bond lengths are very similar to those observed in the two isotypic bis(1,3-bis(2-pyridylimino)isoindoline)cobalt(III) perchlorate methanol solvate complexes mentioned above (space groups C2 and P2₁/c), where the Co—N_imine bond lengths vary from ca 1.885 to 1.890 Å, and the Co—N_pyridine bond lengths vary from ca 1.971 to 1.986 Å.

Figure 1
The molecular structure of the cation of the title complex, with atom labelling and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by the twofold rotation symmetry operation −x + $[{1\over 2}]$ , y, −z + $[{3\over 4}]$ .

On coordination, the ligand molecules are extremely twisted compared to the situation in the free ligand, which is relatively planar with an r.m.s. deviation of 0.061 Å for all 23 non-H atoms (Posel & Stoeckli-Evans, 2018). In the complex cation, the pyridine rings (N4/C6–C10) and (N7/C12–C16) are inclined to the mean plane of the pyrrolopyrazine unit (N1/N2/N5/C1–C5/C11) by 28.3 (3) and 30.9 (3)°, respectively, and by 53.6 (3)° to each other. This arrangement is similar to that observed for the isotypic bis(1,3-bis(2-pyridylimino)isoindoline)cobalt(III) perchlorate methanol solvate complexes mentioned above.

In the crystal, the cations are linked via C—H⋯O_perchlorate and C—H⋯N_acetonitrile hydrogen bonds, forming a supramolecular three-dimensional framework (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯N8	0.93	2.61	3.372 (12)	139
C14—H14⋯O1ⁱ	0.93	2.55	3.256 (13)	133
C16—H16⋯O3ⁱⁱ	0.93	2.51	3.213 (19)	133
C18—H18C⋯O2	0.96	2.42	3.31 (3)	154
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, -z+{\script{1\over 4}}]$ ; (ii) $[y, x+{\script{1\over 2}}, z+{\script{1\over 4}}]$ .

Figure 2
A view along the c axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines [see Table 1

; only the H atoms (grey balls) involved in hydrogen bonding have been included].

There are small cavities in the crystal structure, with a total potential solvent area volume of ca 72 Å³ (ca 1% of the unit-cell volume). They are represented in brown–yellow in Fig. 3. There is no evidence of any residual electron density being present in these cavities on examination of the final difference-Fourier map (see Table 2).

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₁₆H₁₀N₇)₂]ClO₄·2C₂H₃N
M_r	841.11
Crystal system, space group	Tetragonal, I $[\overline{4}]$ 2d
Temperature (K)	293
a, c (Å)	19.9756 (17), 18.3409 (18)
V (Å³)	7318.5 (14)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.61
Crystal size (mm)	0.61 × 0.57 × 0.51

Data collection
Diffractometer	Stoe–Siemens AED2 4-circle
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3245, 3148, 2352
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.113, 0.98
No. of reflections	3148
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.30
Absolute structure	Flack x determined using 815 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.05 (3)
Computer programs: STADI4 and X-RED (Stoe & Cie, 1997 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Figure 3
A view along the c axis of the crystal packing of the title compound. The small cavities in the crystal structure are represented in yellow–brown (Mercury; Macrae et al., 2008

Synthesis and crystallization

The title compound was synthesized by the reaction of (5Z,7Z)-N⁵,N⁷-di(pyridin-2-yl)-5H-pyrrolo[3,4-b]pyrazine-5,7(6H)-diimine (L) (Posel & Stoeckli-Evans, 2018) with Co(ClO₄)₂.

In a round-bottomed flask were mixed 0.0646 g (0.00021 mol) of ligand L in 7 ml of dry methanol and 0.1 ml of triethylamine. Then a solution of 0.0366 g (0.0001 mol) of Co(ClO₄)₂·6H₂O in 3 ml of dry methanol was added. The mixture was stirred at room temperature for 48 h. The main product, a brown–black powder, was filtered off and dried in a vacuum desiccator over silica (yield ∼0.03 g, 36%; m.p. >623 K). This solid was then used for recrystallization from a mixture of acetonitrile/methanol (1/1, v/v), which gave a small amount of brown–black block-like crystals. Analysis for [(C₁₆H₁₀N₇)₂Co]·ClO₄·2(CH₃CN) (840.0931 g mol⁻¹): calculated C 51.47, H 3.12, N 26.65%; found C 50.68, H 3.11, N 26.18%. IR (KBr pellet. cm⁻¹): 2244, 1611, 1579, 1537, 1450, 1359, 1221, 1144, 1089, 782, 748, 650, 548, 437.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The Cl atom of the perchlorate anion is located on a fourfold rotoinversion axis, and two O atoms (O2 and O3) are partially disordered (occupancies of 0.5 each). The intensity data were measured at room temperature using a four-circle diffractometer. No absorption correction was applied as there were no suitable reflections for ψ scans.

Structural data

CCDC reference: 1844111

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S241431461800754X/bh4036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461800754X/bh4036Isup2.hkl

checkCIF report

Computing details top

Data collection: STADI4 (Stoe & Cie, 1997); cell refinement: STADI4 (Stoe & Cie, 1997); data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Bis[N⁵,N⁷-bis(pyridin-2-yl)-6,7-dihydro-5H-pyrrolo[3,4-b]pyrazine-5,7-diimine]cobalt(III) perchlorate acetonitrile disolvate top

Crystal data top

[Co(C₁₆H₁₀N₇)₂]ClO₄·2C₂H₃N	D_x = 1.527 Mg m⁻³
M_r = 841.11	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 18 reflections
a = 19.9756 (17) Å	θ = 14.0–17.5°
c = 18.3409 (18) Å	µ = 0.61 mm⁻¹
V = 7318.5 (14) Å³	T = 293 K
Z = 8	Block, brown–black
F(000) = 3440	0.61 × 0.57 × 0.51 mm

Data collection top

Stoe–Siemens AED2 4-circle diffractometer	R_int = 0.046
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.0°
Plane graphite monochromator	h = −16→16
ω/2θ scans	k = 0→23
3245 measured reflections	l = 0→21
3148 independent reflections	2 standard reflections every 60 min
2352 reflections with I > 2σ(I)	intensity decay: 2%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0532P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max = 0.001
3148 reflections	Δρ_max = 0.28 e Å⁻³
273 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 815 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (3)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.250000	0.32578 (6)	0.375000	0.0317 (3)
N1	0.4124 (3)	0.3449 (3)	0.1426 (3)	0.0523 (16)
N2	0.4962 (3)	0.2988 (3)	0.2590 (3)	0.0496 (16)
N3	0.4069 (3)	0.2768 (3)	0.3910 (3)	0.0383 (13)
N4	0.2948 (3)	0.2569 (3)	0.4357 (3)	0.0356 (12)
N5	0.3249 (3)	0.3256 (3)	0.3125 (2)	0.0333 (12)
N6	0.2759 (3)	0.3747 (3)	0.2050 (3)	0.0410 (14)
N7	0.2088 (3)	0.3960 (3)	0.3135 (3)	0.0355 (13)
C1	0.4774 (4)	0.3335 (4)	0.1360 (4)	0.059 (2)
H1	0.496793	0.340028	0.090421	0.071*
C2	0.5184 (4)	0.3124 (4)	0.1922 (4)	0.056 (2)
H2	0.563872	0.307431	0.182886	0.067*
C3	0.4310 (3)	0.3115 (3)	0.2660 (4)	0.0373 (16)
C4	0.3912 (3)	0.3331 (3)	0.2099 (3)	0.0375 (16)
C5	0.3881 (3)	0.3036 (3)	0.3308 (3)	0.0338 (16)
C6	0.3625 (3)	0.2532 (4)	0.4425 (3)	0.0388 (15)
C7	0.3912 (4)	0.2167 (4)	0.5000 (4)	0.061 (2)
H7	0.437456	0.216834	0.505894	0.074*
C8	0.3531 (4)	0.1815 (5)	0.5469 (4)	0.068 (3)
H8	0.372497	0.158673	0.585743	0.082*
C9	0.2845 (4)	0.1798 (4)	0.5360 (4)	0.059 (2)
H9	0.257089	0.154050	0.565874	0.071*
C10	0.2578 (4)	0.2170 (3)	0.4802 (4)	0.0450 (17)
H10	0.211885	0.214784	0.472461	0.054*
C11	0.3235 (4)	0.3455 (3)	0.2405 (3)	0.0355 (15)
C12	0.2207 (3)	0.4021 (3)	0.2399 (4)	0.0361 (16)
C13	0.1813 (4)	0.4438 (3)	0.1971 (4)	0.0410 (17)
H13	0.187905	0.445373	0.146947	0.049*
C14	0.1324 (4)	0.4828 (4)	0.2286 (4)	0.0503 (19)
H14	0.104580	0.509249	0.199938	0.060*
C15	0.1255 (4)	0.4820 (4)	0.3025 (4)	0.0489 (19)
H15	0.096083	0.511310	0.325368	0.059*
C16	0.1623 (3)	0.4377 (3)	0.3429 (4)	0.0406 (17)
H16	0.155166	0.436012	0.392920	0.049*
N8	0.1199 (5)	0.1258 (4)	0.4430 (5)	0.097 (3)
C17	0.0661 (6)	0.1296 (5)	0.4271 (5)	0.072 (3)
C18	−0.0026 (5)	0.1357 (6)	0.4052 (6)	0.092 (3)
H18A	−0.013282	0.182072	0.398060	0.138*
H18B	−0.030970	0.117374	0.442438	0.138*
H18C	−0.009440	0.111691	0.360476	0.138*
Cl1	0.000000	0.000000	0.21977 (17)	0.0721 (9)
O1	0.0549 (4)	0.0048 (9)	0.1770 (6)	0.185 (5)
O2	−0.0216 (13)	0.011 (2)	0.2881 (8)	0.175 (12)	0.5
O3	−0.0089 (16)	0.0710 (8)	0.2249 (8)	0.179 (11)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0355 (7)	0.0326 (7)	0.0270 (6)	0.000	−0.0011 (6)	0.000
N1	0.061 (4)	0.058 (4)	0.038 (4)	0.008 (3)	0.012 (3)	0.003 (3)
N2	0.040 (3)	0.056 (4)	0.053 (4)	0.004 (3)	0.003 (3)	0.000 (3)
N3	0.037 (3)	0.041 (3)	0.037 (3)	−0.001 (2)	−0.007 (3)	0.007 (3)
N4	0.041 (3)	0.035 (3)	0.031 (3)	−0.002 (3)	0.002 (2)	0.002 (3)
N5	0.036 (3)	0.037 (3)	0.027 (3)	0.004 (3)	−0.002 (3)	0.000 (2)
N6	0.047 (3)	0.044 (3)	0.032 (3)	0.010 (3)	−0.003 (3)	0.002 (3)
N7	0.038 (3)	0.033 (3)	0.035 (3)	0.001 (3)	0.001 (3)	0.002 (3)
C1	0.060 (5)	0.073 (5)	0.044 (5)	0.008 (4)	0.025 (4)	0.000 (4)
C2	0.045 (5)	0.069 (6)	0.054 (5)	0.002 (4)	0.016 (4)	0.005 (4)
C3	0.040 (4)	0.032 (4)	0.041 (4)	−0.003 (3)	0.003 (3)	−0.002 (3)
C4	0.051 (4)	0.033 (4)	0.029 (4)	0.004 (3)	0.005 (3)	−0.003 (3)
C5	0.035 (4)	0.031 (4)	0.035 (4)	0.001 (3)	−0.003 (3)	−0.003 (3)
C6	0.043 (4)	0.036 (4)	0.037 (4)	0.000 (4)	−0.003 (3)	0.004 (3)
C7	0.055 (5)	0.073 (5)	0.056 (5)	−0.004 (4)	−0.010 (4)	0.022 (5)
C8	0.067 (6)	0.089 (7)	0.049 (5)	0.009 (5)	−0.004 (4)	0.039 (5)
C9	0.073 (6)	0.049 (5)	0.054 (5)	0.006 (4)	0.014 (4)	0.023 (4)
C10	0.056 (5)	0.033 (3)	0.045 (4)	0.000 (4)	0.008 (4)	0.008 (3)
C11	0.044 (4)	0.036 (4)	0.026 (3)	0.003 (3)	0.000 (3)	−0.004 (3)
C12	0.038 (4)	0.035 (4)	0.035 (4)	−0.003 (3)	−0.004 (3)	0.001 (3)
C13	0.047 (4)	0.040 (4)	0.036 (4)	−0.002 (3)	−0.004 (3)	0.011 (3)
C14	0.040 (4)	0.050 (5)	0.061 (5)	0.005 (4)	−0.013 (4)	0.019 (4)
C15	0.047 (5)	0.036 (4)	0.063 (5)	0.008 (3)	0.004 (4)	0.008 (4)
C16	0.037 (4)	0.040 (4)	0.045 (4)	0.005 (3)	0.003 (3)	0.000 (3)
N8	0.091 (6)	0.081 (6)	0.118 (8)	−0.002 (6)	−0.028 (6)	−0.002 (6)
C17	0.087 (8)	0.063 (6)	0.067 (6)	−0.002 (6)	−0.009 (6)	−0.015 (5)
C18	0.070 (7)	0.111 (8)	0.096 (8)	−0.010 (6)	−0.009 (6)	−0.027 (7)
Cl1	0.059 (2)	0.108 (3)	0.0493 (18)	0.010 (2)	0.000	0.000
O1	0.067 (5)	0.343 (17)	0.146 (8)	−0.008 (8)	0.010 (6)	0.002 (10)
O2	0.19 (3)	0.26 (3)	0.075 (10)	0.08 (2)	0.008 (12)	−0.076 (19)
O3	0.40 (4)	0.071 (11)	0.066 (10)	0.060 (16)	0.005 (17)	0.004 (9)

Geometric parameters (Å, º) top

Co1—N5ⁱ	1.885 (5)	C7—H7	0.9300
Co1—N5	1.885 (5)	C8—C9	1.386 (11)
Co1—N7	1.979 (5)	C8—H8	0.9300
Co1—N7ⁱ	1.979 (5)	C9—C10	1.372 (10)
Co1—N4	1.983 (6)	C9—H9	0.9300
Co1—N4ⁱ	1.983 (6)	C10—H10	0.9300
N1—C1	1.325 (9)	C12—C13	1.389 (9)
N1—C4	1.326 (8)	C13—C14	1.375 (10)
N2—C2	1.331 (9)	C13—H13	0.9300
N2—C3	1.332 (8)	C14—C15	1.363 (11)
N3—C5	1.284 (8)	C14—H14	0.9300
N3—C6	1.378 (8)	C15—C16	1.368 (9)
N4—C10	1.359 (8)	C15—H15	0.9300
N4—C6	1.361 (8)	C16—H16	0.9300
N5—C5	1.378 (8)	N8—C17	1.116 (11)
N5—C11	1.381 (7)	C17—C18	1.436 (14)
N6—C11	1.291 (8)	C18—H18A	0.9600
N6—C12	1.387 (8)	C18—H18B	0.9600
N7—C16	1.357 (8)	C18—H18C	0.9600
N7—C12	1.377 (8)	Cl1—O2ⁱⁱ	1.343 (15)
C1—C2	1.383 (11)	Cl1—O2	1.343 (15)
C1—H1	0.9300	Cl1—O1	1.352 (9)
C2—H2	0.9300	Cl1—O1ⁱⁱ	1.352 (9)
C3—C4	1.371 (9)	Cl1—O3	1.433 (16)
C3—C5	1.473 (9)	Cl1—O3ⁱⁱ	1.433 (16)
C4—C11	1.485 (9)	O2—O2ⁱⁱ	0.96 (4)
C6—C7	1.406 (10)	O2—O3	1.69 (4)
C7—C8	1.346 (11)

N5ⁱ—Co1—N5	179.7 (3)	C9—C8—H8	120.7
N5ⁱ—Co1—N7	91.0 (2)	C10—C9—C8	118.6 (8)
N5—Co1—N7	89.2 (2)	C10—C9—H9	120.7
N5ⁱ—Co1—N7ⁱ	89.2 (2)	C8—C9—H9	120.7
N5—Co1—N7ⁱ	91.0 (2)	N4—C10—C9	123.7 (7)
N7—Co1—N7ⁱ	89.7 (3)	N4—C10—H10	118.1
N5ⁱ—Co1—N4	90.9 (2)	C9—C10—H10	118.1
N5—Co1—N4	88.9 (2)	N6—C11—N5	128.9 (6)
N7—Co1—N4	177.8 (2)	N6—C11—C4	123.8 (6)
N7ⁱ—Co1—N4	89.1 (2)	N5—C11—C4	107.1 (6)
N5ⁱ—Co1—N4ⁱ	88.9 (2)	N7—C12—N6	123.7 (6)
N5—Co1—N4ⁱ	90.9 (2)	N7—C12—C13	120.6 (6)
N7—Co1—N4ⁱ	89.1 (2)	N6—C12—C13	115.3 (6)
N7ⁱ—Co1—N4ⁱ	177.8 (2)	C14—C13—C12	120.3 (7)
N4—Co1—N4ⁱ	92.1 (3)	C14—C13—H13	119.8
C1—N1—C4	111.6 (7)	C12—C13—H13	119.8
C2—N2—C3	112.0 (6)	C15—C14—C13	118.9 (7)
C5—N3—C6	122.9 (6)	C15—C14—H14	120.6
C10—N4—C6	116.9 (6)	C13—C14—H14	120.6
C10—N4—Co1	120.0 (5)	C14—C15—C16	119.4 (7)
C6—N4—Co1	122.5 (5)	C14—C15—H15	120.3
C5—N5—C11	110.1 (5)	C16—C15—H15	120.3
C5—N5—Co1	125.5 (4)	N7—C16—C15	123.4 (7)
C11—N5—Co1	124.4 (4)	N7—C16—H16	118.3
C11—N6—C12	122.1 (5)	C15—C16—H16	118.3
C16—N7—C12	116.9 (6)	N8—C17—C18	178.5 (14)
C16—N7—Co1	119.6 (4)	C17—C18—H18A	109.5
C12—N7—Co1	123.3 (5)	C17—C18—H18B	109.5
N1—C1—C2	124.4 (7)	H18A—C18—H18B	109.5
N1—C1—H1	117.8	C17—C18—H18C	109.5
C2—C1—H1	117.8	H18A—C18—H18C	109.5
N2—C2—C1	123.5 (7)	H18B—C18—H18C	109.5
N2—C2—H2	118.2	O2ⁱⁱ—Cl1—O2	42.0 (16)
C1—C2—H2	118.2	O2ⁱⁱ—Cl1—O1	107.0 (12)
N2—C3—C4	123.7 (6)	O2—Cl1—O1	142.4 (15)
N2—C3—C5	128.7 (6)	O2ⁱⁱ—Cl1—O1ⁱⁱ	142.4 (15)
C4—C3—C5	107.5 (6)	O2—Cl1—O1ⁱⁱ	107.0 (12)
N1—C4—C3	124.7 (6)	O1—Cl1—O1ⁱⁱ	109.0 (9)
N1—C4—C11	127.8 (6)	O2ⁱⁱ—Cl1—O3	97.7 (19)
C3—C4—C11	107.3 (5)	O2—Cl1—O3	75.1 (18)
N3—C5—N5	127.5 (6)	O1—Cl1—O3	94.0 (14)
N3—C5—C3	124.7 (6)	O1ⁱⁱ—Cl1—O3	90.4 (13)
N5—C5—C3	107.7 (5)	O2ⁱⁱ—Cl1—O3ⁱⁱ	75.1 (18)
N4—C6—N3	124.0 (6)	O2—Cl1—O3ⁱⁱ	97.7 (19)
N4—C6—C7	120.1 (6)	O1—Cl1—O3ⁱⁱ	90.4 (13)
N3—C6—C7	115.4 (6)	O1ⁱⁱ—Cl1—O3ⁱⁱ	94.0 (14)
C8—C7—C6	121.4 (8)	O3—Cl1—O3ⁱⁱ	172.5 (13)
C8—C7—H7	119.3	O2ⁱⁱ—O2—Cl1	69.0 (8)
C6—C7—H7	119.3	O2ⁱⁱ—O2—O3	100 (4)
C7—C8—C9	118.7 (8)	Cl1—O2—O3	54.9 (13)
C7—C8—H8	120.7	Cl1—O3—O2	50.0 (10)

N7—Co1—N5—C5	157.8 (5)	C6—N4—C10—C9	7.6 (10)
N7ⁱ—Co1—N5—C5	68.1 (5)	Co1—N4—C10—C9	−163.8 (5)
N4—Co1—N5—C5	−21.0 (5)	C8—C9—C10—N4	−1.6 (12)
N4ⁱ—Co1—N5—C5	−113.1 (5)	C12—N6—C11—N5	12.3 (10)
N7—Co1—N5—C11	−24.6 (5)	C12—N6—C11—C4	−161.7 (6)
N7ⁱ—Co1—N5—C11	−114.3 (5)	C5—N5—C11—N6	−172.9 (6)
N4—Co1—N5—C11	156.6 (5)	Co1—N5—C11—N6	9.2 (9)
N4ⁱ—Co1—N5—C11	64.5 (5)	C5—N5—C11—C4	1.9 (7)
C4—N1—C1—C2	−0.6 (11)	Co1—N5—C11—C4	−176.0 (4)
C3—N2—C2—C1	−3.5 (11)	N1—C4—C11—N6	−4.7 (11)
N1—C1—C2—N2	2.7 (13)	C3—C4—C11—N6	170.5 (6)
C2—N2—C3—C4	2.8 (10)	N1—C4—C11—N5	−179.9 (6)
C2—N2—C3—C5	−179.5 (7)	C3—C4—C11—N5	−4.6 (7)
C1—N1—C4—C3	−0.2 (10)	C16—N7—C12—N6	165.1 (6)
C1—N1—C4—C11	174.3 (7)	Co1—N7—C12—N6	−20.1 (9)
N2—C3—C4—N1	−1.1 (11)	C16—N7—C12—C13	−7.1 (9)
C5—C3—C4—N1	−179.2 (6)	Co1—N7—C12—C13	167.8 (5)
N2—C3—C4—C11	−176.5 (6)	C11—N6—C12—N7	−5.7 (10)
C5—C3—C4—C11	5.4 (7)	C11—N6—C12—C13	166.8 (6)
C6—N3—C5—N5	13.9 (11)	N7—C12—C13—C14	4.1 (10)
C6—N3—C5—C3	−161.2 (6)	N6—C12—C13—C14	−168.6 (6)
C11—N5—C5—N3	−174.4 (6)	C12—C13—C14—C15	2.9 (11)
Co1—N5—C5—N3	3.4 (10)	C13—C14—C15—C16	−6.7 (12)
C11—N5—C5—C3	1.4 (7)	C12—N7—C16—C15	3.3 (10)
Co1—N5—C5—C3	179.3 (4)	Co1—N7—C16—C15	−171.8 (6)
N2—C3—C5—N3	−6.4 (11)	C14—C15—C16—N7	3.6 (11)
C4—C3—C5—N3	171.6 (6)	O1—Cl1—O2—O2ⁱⁱ	−43 (7)
N2—C3—C5—N5	177.6 (6)	O1ⁱⁱ—Cl1—O2—O2ⁱⁱ	154 (5)
C4—C3—C5—N5	−4.4 (7)	O3—Cl1—O2—O2ⁱⁱ	−120 (6)
C10—N4—C6—N3	163.4 (6)	O3ⁱⁱ—Cl1—O2—O2ⁱⁱ	57 (5)
Co1—N4—C6—N3	−25.4 (10)	O2ⁱⁱ—Cl1—O2—O3	120 (6)
C10—N4—C6—C7	−8.6 (10)	O1—Cl1—O2—O3	77 (2)
Co1—N4—C6—C7	162.6 (6)	O1ⁱⁱ—Cl1—O2—O3	−85.8 (18)
C5—N3—C6—N4	−1.4 (11)	O3ⁱⁱ—Cl1—O2—O3	177.6 (4)
C5—N3—C6—C7	170.9 (7)	O2ⁱⁱ—Cl1—O3—O2	−36 (3)
N4—C6—C7—C8	4.0 (13)	O1—Cl1—O3—O2	−143.4 (14)
N3—C6—C7—C8	−168.7 (8)	O1ⁱⁱ—Cl1—O3—O2	107.5 (13)
C6—C7—C8—C9	2.2 (14)	O2ⁱⁱ—O2—O3—Cl1	55 (4)
C7—C8—C9—C10	−3.4 (14)

Symmetry codes: (i) −x+1/2, y, −z+3/4; (ii) −x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N8	0.93	2.61	3.372 (12)	139
C14—H14···O1ⁱⁱⁱ	0.93	2.55	3.256 (13)	133
C16—H16···O3^iv	0.93	2.51	3.213 (19)	133
C18—H18C···O2	0.96	2.42	3.31 (3)	154

Symmetry codes: (iii) x, −y+1/2, −z+1/4; (iv) y, x+1/2, z+1/4.

Funding information

We are grateful to the Swiss National Science Foundation and the University of Neuchâtel for financial support.

References

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