Investigation of nitro–nitrito photoisomerization: crystal structure of trans-chlorido­nitro­(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4N,N′,N′′,N′′′)cobalt(III) chloride

Ohba, S.; Tsuchimoto, M.; Yamada, N.

doi:10.1107/S205698901801678X

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Volume 74| Part 12| December 2018| Pages 1908-1912

https://doi.org/10.1107/S205698901801678X

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Investigation of nitro–nitrito photoisomerization: crystal structure of trans-chloridonitro(1,4,8,11-tetraazacyclotetradecane-κ⁴N,N′,N′′,N′′′)cobalt(III) chloride

Shigeru Ohba,^a ^* Masanobu Tsuchimoto ^b and Naoki Yamada ^c

^aResearch and Education Center for Natural Sciences, Keio University, 4-1-1 Hiyoshi, Kohoku-ku, Yokohama 223-8521, Japan, ^bDepartment of Chemistry, Chiba Institute of Technology, Shibazono 2-1-1, Narashino, Chiba 275-0023, Japan, and ^cDepartment of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan
^*Correspondence e-mail: ohba@a3.keio.jp

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 November 2018; accepted 26 November 2018; online 30 November 2018)

The reaction cavity of the nitro group in the crystal of the title compound, [CoCl(NO₂)(C₁₀H₂₄N₄)]Cl, (I), was investigated to confirm that it offers sufficient free space for linkage isomerization to occur in accordance with the observed photochemical reactivity. The complex cation has crystallographic 2/m symmetry and the nitro and chloro ligands at the trans positions are statistically disordered. The complete cyclam ligand is generated by symmetry from a quarter of the molecule. In the crystal of (I), the complex cations and Cl⁻ ions are linked into a three-dimensional network by N—H⋯Cl(counter-ion) hydrogen bonds.

Keywords: crystal structure; nitro-nitrito photo-isomerization; reaction cavity.

CCDC reference: 1881114

1. Chemical context

The photochemical reactions of metal complexes in the solid state attract much attention from crystallographers and chemists (Coppens et al., 2002 ; Vittal & Quah, 2017 ). The present authors have investigated photochemical linkage isomerization of a series of the nitrocobalt(III) complexes, trans-[Co(en)₂(NO₂)(NCS)]Cl·H₂O and other salts, (Ohba, Tsuchimoto & Kurachi, 2018 ), trans-[Co(acac)₂(NO₂)(pyridine derivative)] (Ohba, Tsuchimoto & Miyazaki, 2018 ), and trans-[Co(salen)(NO₂)(pyridine derivative)] (Ohba, Tsuchimoto & Yamada, 2018 ). In the present study, we describe our investigations of another type of nitrocobalt complex, trans-[Co(cyclam)(NO₂)Cl]Cl, (I), where cyclam stands for 1,4,8,11-tetraazacyclotetradecane. It is known that the stability of the nitrito–Co^III complexes greatly depends on the electronic effects of the co-existing ligands, and cyclam is expected to bring a small rate constant of the nitrito-to-nitro thermal reaction (Miyoshi et al., 1983 ). The crystal structure of trans-[Co(cyclam)(NO₂)₂]ClO₄, (II), has already been reported by Ohba et al. (2001 ). For (II) and the related PF₆ salt, thermal conversion steps from the dinitrito to dinitro form were investigated by differential scanning calorimetry and DFT calculations (Eslami et al., 2014 ).

When a KBr disk of (I) was irradiated for 30 min with a Xe lamp, the IR spectrum showed an apparent change involving an increase in intensity of the absorption peak of ca 1000 cm⁻¹ (see the Figure in the supporting information), which corresponds to the symmetric N—O stretching mode of the nitrito form (Eslami et al., 2014). The IR spectrum of the irradiated complex was almost unchanged on standing at room temperature for 2 h, indicating the long life-time of the nitrito form as in (II), and reverted to that before irradiation by heating at 55°C for 45 min. The crystal structure of (I) was determined to establish the dimensions of the reaction cavity and steric circumstance of the nitro group, and to compare them with those in (II).

2. Structural commentary

The molecular structure of (I) is shown in Fig. 1. The coordination geometry around the Co atom is a distorted octahedron with the N5 (nitro) and Cl2 atoms at the trans positions. The macrocyclic ligand cyclam adopts the trans-III conformation of Tobe's classification (Bosnich et al., 1965 ). The metal atom lies at site symmetry 2/m, and the atoms N5, Cl2 and C9 (the central C atom in the six-membered chelate ring) also lie on the mirror plane. There is a twofold axis running through the Co1 atom and midpoint of the C7—C7ⁱⁱⁱ bond in the five-membered chelate ring of cyclam, indicating that the positions of the Cl2 and nitro N5 atoms are exchanged. Similar orientational disorder of the chloridonitrocobalt complexes is observed for trans-[Co(en)₂Cl(NO₂)]ClO₄ (Ohba & Eishima, 2000a ) and the NO₃ salt (Ohba & Eishima, 2000b ).

Figure 1
The molecular structure of (I)

, showing displacement ellipsoids at the 30% probability level. A crystallographic twofold axis runs through atom Co1 and the midpoint of the C7—C7ⁱⁱⁱ bond. Only one of two possible orientations of the nitro and chloride ions is shown for clarity. Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) x, y, −z + 1; (iii) −x + 1, −y, z.

The Co—N(nitro) bond length is 1.9601 (10) Å, which is the result of restraint in the refinement of disorder, the length being similar to those in (II), 1.962 (5) and 1.968 (5) Å (Ohba, et al., 2001). On the other hand, the Co—Cl bond distance is 2.2513 (12) Å, which is similar to that observed in trans-[Co(cyclam)Cl₂]Cl, 2.2533 (4) Å (Ivaniková et al., 2006 ). There are intramolecular C—H⋯O/Cl hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6⋯Cl3	0.98	2.64	3.3671 (16)	131
C7—H7A⋯O4	0.97	2.28	2.929 (5)	124
C8—H8B⋯Cl2ⁱ	0.97	2.80	3.302 (4)	113
Symmetry code: (i) -x+1, -y, -z+1.

3. Supramolecular features

The crystal structure of (I) is shown in Fig. 2. The complex cations and chloride ions are connected by N—H⋯Cl(counter-ion) hydrogen bonds, forming a three-dimensional network. In (II), there are two independent nitro ligands at the trans positions, and the O atoms of each nitro group show two possible positions (occupation factors 65 and 35%; Ohba, et al., 2001). In the following discussion, the minor O(nitro) atoms will be neglected in (II). Slices of the reaction cavities around the NO₂⁻ group near its plane in (I) and (II) are compared in Fig. 3, where the radii of neighboring atoms are assumed to be 1.0 Å greater than the corresponding van der Waals radii (Bondi, 1964 ), except for Co, its radius being set to 1.90 Å. The shape of the cavity in the nitro plane is mainly defined by the N/C—H⋯O(nitro) contacts which are shown in Figs. 4 and 5. Since the radius of the neighboring H atoms is assumed to be 2.20 Å, the cavity around the nitro O atoms is narrow in the intra- and intermolecular hydrogen-bond directions. In (I), the cavity has sufficient free space to both side of the nitro O atoms for rotation to become the nitrito form, as suggested by the observed photoreactivity. In (II), the cavities of the nitro groups have space at one of the O atoms for conversion to the mono- and di-nitrito forms. The bifurcated N—H⋯O,O hydrogen bonds form an R₂²(4) ring (Fig. 5), which is also observed in the salts of trans-[Co(en)₂(NO₂)(NCS)]⁺ complexes (Ohba, Tsuchimoto & Kurachi, 2018)

Figure 2
The crystal structure of (I)

, projected along b. The N—H⋯Cl hydrogen bonds are shown as red dashed lines. Only one of two possible orientations of the complex cation is shown for clarity.

Figure 3
Comparison of the slices of the cavity around the nitro group within 0.1 Å from the plane in (I)

and (II), where the minor O atoms (occupancy 35%) of each nitro ligand are omitted for clarity in (II). Symmetry codes for (I)

: (i) −x + 1, −y, −z + 1; (ii) x, y, −z + 1; (iii) −x + 1, −y, z.

Figure 4
The steric circumstances of the nitro group in (I)

. Only parts of the complex are shown for clarity. The nitro group may be replaced with the Cl ligand due to the orientational disorder. There is a crystallographic twofold axis running vertical through the Co1^xii and Co1^xv atoms, another C8/C9 equivalent moiety which lies below the planes of the nitro groups being omitted for clarity. The N/C—H⋯O hydrogen bonds are shown as blue dashed lines. The other O⋯H contacts shorter than 2.9 Å (O4⋯H7B^x = 2.78 Å and O4⋯H8B^iv = 2.85 Å) are indicated as green dashed lines, and those of rather long distances (O4⋯H9B^iv = 3.11 Å and O4^vi⋯H9A^iv = 3.09 Å) are indicated as orange dashed lines. Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) x, y, −z + 1; (iii) −x + 1, −y, z; (iv) −x, −y, z; (v) −x, −y, −z + 1; (vi) −x, −y − 1, z; (vii) −x, −y − 1, −z + 1; (viii) x − 1, y − 1, z; (ix) x − 1, y − 1, −z + 1; (x) y, −x, −z + $[{3\over 2}]$ ; (xi) −y, x − 1, −z + $[{3\over 2}]$ ; (xii) −y, x − 1, z + $[{1\over 2}]$ ; (xiii) y, −x, z − $[{1\over 2}]$ ; (xiv) −y, x − 1, z − $[{1\over 2}]$ .

Figure 5
The steric circumstance of the nitro groups in (II). The minor O atoms (occupancy 35%) of each nitro ligand are omitted, and only parts of the complex are shown for clarity. The N/C—H⋯O hydrogen bonds are shown as blue dashed lines (H⋯O distances 2.13–2.29 Å). A green dashed line indicates the O8ⁱ⋯H22B contact of 2.63 Å. Other O⋯H contacts of rather long distances (3.03–3.09 Å) are indicated as orange dashed lines. Symmetry code: (i) x, y, z + 1.

4. Database survey

There is no entry for a (cyclam)nitrocobalt(III) complex in the Cambridge Structural Database (CSD Version 5.39; Groom et al., 2016 ), except for trans-[Co(cyclam)(NO₂)₂]ClO₄ (Ohba et al., 2001). The nitrito coordination was reported for certain Co^III complexes with cyclam derivatives, for example trans-[Co(Me₈[14]ane)(ONO)₂]ClO₄ (Horn et al., 2001 ), where Me₈[14]ane stands for 3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane, and trans-[Co(L)(NO₂)(ONO)]ClO₄ and cis-[Co(L)(NO₂)(ONO)]ClO₄ (Boyd et al., 2007 ), where L stands for 1-(anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane.

The structures of trans-dichloro complexes have been published for several salts, i.e. trans-[Co(cyclam)Cl₂](Cl⁻)_1.47(H₃O⁺)_0.47(H₂O)_3.53 (Sosa-Torres et al., 1997 ), trans-[Co(cyclam)Cl₂]Cl (Ivaniková et al., 2006), trans-[Co(cyclam)Cl₂]PF₆ and trans-[Co(cyclam)Cl₂]Tf₂N, where Tf₂N⁻ is bis(trifluoromethanesulfonyl)amide anion (Oba & Mochida, 2015 ), the conformation of cyclam in these crystals being trans-III according to Tobe's classification (Bosnich et al., 1965). The (cyclam)chlorocobalt(III) alkynyl complexes such as trans-[Co(cyclam)Cl(1-ethynylnaphthalene)]CF₃SO₃·OEt₂ (Judkins et al., 2018 ) have been studied for their structural and spectroscopic properties.

5. Synthesis and crystallization

trans-[Co(cyclam)Cl₂]Cl was prepared by a literature method (Nakahara & Shibata, 1977 ) from cobalt(II) chloride hexahydrate and cyclam, and converted to trans-[Co(cyclam)Cl(NH₃)]Cl₂·H₂O according to the method of Lee & Poon (1973 ). Then, trans-[Co(cyclam)Cl(NH₃)]Cl₂·H₂O (1.0 mmol) was dissolved in 11 ml of 1% NH₃ aqueous solution and neutralized with diluted HCl. To the solution sodium nitrite (8.0 mmol) and 1 ml of 1 M HCl were added, and the reaction mixture was stirred for 3 h at room temperature, and concentrated to precipitate the title compound, (I). Orange-red plate-like crystals of (I) were grown from a dimethyl sulfoxide solution by diffusion of diethyl ether vapour.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The electron densities of the nitro N5 and Cl2 atoms overlap with each other because of the orientational disorder of the complex cation. An EADP command was used for atoms N5 and Cl2, and the Co1—N5 bond distance was restrained to be 1.960 Å (s.u. = 0.001 Å) to obtain a reasonable geometry for the nitro group. The H atoms bound to C and N were positioned geometrically. They were refined as riding, with C—H/N—H = 0.97–0.98 Å, and U_iso(H) = 1.2U_eq(C/N). One reflection showing poor agreement was omitted from the final refinement.

Table 2
Experimental details

Crystal data
Chemical formula	[CoCl(NO₂)(C₁₀H₂₄N₄)]Cl
M_r	376.17
Crystal system, space group	Tetragonal, P4₂/m
Temperature (K)	301
a, c (Å)	7.6052 (3), 13.3873 (7)
V (Å³)	774.31 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.46
Crystal size (mm)	0.25 × 0.25 × 0.10

Data collection
Diffractometer	Bruker D8 VENTURE
Absorption correction	Integration (SADABS; Bruker, 2016 )
T_min, T_max	0.704, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	7967, 953, 922
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.079, 1.19
No. of reflections	953
No. of parameters	58
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.26
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ), CAVITY (Ohashi et al., 1981 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1881114

Crystal structure: contains datablocks I, general. DOI: https://doi.org/10.1107/S205698901801678X/hb7787sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901801678X/hb7787Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901801678X/hb7787Isup4.cdx

The IR spectra of chloro (I) and dinitro (II) complexes before and after photoirradiation for 30 min with a 150 W Xe lamp to the KBr disk, and after further standing for 2h. DOI: https://doi.org/10.1107/S205698901801678X/hb7787sup3.tif

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008) and CAVITY (Ohashi et al., 1981); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010).

trans-Chloridonitro(1,4,8,11-tetraazacyclotetradecane-\ κ⁴N,N ',N '',N ''')cobalt(III) chloride top

Crystal data top

[CoCl(NO₂)(C₁₀H₂₄N₄)]Cl	D_x = 1.613 Mg m⁻³
M_r = 376.17	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₂/m	Cell parameters from 6699 reflections
a = 7.6052 (3) Å	θ = 2.7–27.9°
c = 13.3873 (7) Å	µ = 1.46 mm⁻¹
V = 774.31 (7) Å³	T = 301 K
Z = 2	Plate, orange
F(000) = 392	0.25 × 0.25 × 0.10 mm

Data collection top

Bruker D8 VENTURE diffractometer	922 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.028
Absorption correction: integration (SADABS; Bruker, 2016)	θ_max = 27.9°, θ_min = 2.7°
T_min = 0.704, T_max = 0.876	h = −9→10
7967 measured reflections	k = −10→9
953 independent reflections	l = −15→17

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0224P)² + 0.627P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max < 0.001
S = 1.19	Δρ_max = 0.44 e Å⁻³
953 reflections	Δρ_min = −0.26 e Å⁻³
58 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.056 (7)
Primary atom site location: structure-invariant direct methods

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.5000	0.0000	0.5000	0.02498 (19)
Cl2	0.7410 (3)	0.1720 (4)	0.5000	0.0336 (3)	0.5
Cl3	0.5000	0.5000	0.7500	0.0529 (3)
O4	0.2278 (5)	−0.2075 (6)	0.5775 (3)	0.0664 (11)	0.5
N5	0.2929 (11)	−0.1534 (15)	0.5000	0.0336 (3)	0.5
N6	0.4033 (2)	0.1478 (2)	0.60785 (13)	0.0352 (4)
H6	0.4853	0.2464	0.6151	0.042*
C7	0.4146 (4)	0.0476 (3)	0.70245 (16)	0.0519 (6)
H7A	0.3180	−0.0353	0.7071	0.062*
H7B	0.4085	0.1269	0.7591	0.062*
C8	0.2278 (3)	0.2279 (3)	0.5944 (2)	0.0535 (6)
H8A	0.2023	0.3034	0.6510	0.064*
H8B	0.1396	0.1358	0.5927	0.064*
C9	0.2167 (5)	0.3338 (5)	0.5000	0.0618 (11)
H9A	0.3113	0.4194	0.5000	0.074*
H9B	0.1066	0.3981	0.5000	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0221 (3)	0.0253 (3)	0.0275 (3)	0.00039 (16)	0.000	0.000
Cl2	0.0237 (10)	0.0297 (8)	0.0476 (6)	−0.0111 (5)	0.000	0.000
Cl3	0.0454 (4)	0.0454 (4)	0.0678 (8)	0.000	0.000	0.000
O4	0.054 (2)	0.075 (3)	0.071 (2)	−0.0275 (19)	0.0046 (19)	0.004 (2)
N5	0.0237 (10)	0.0297 (8)	0.0476 (6)	−0.0111 (5)	0.000	0.000
N6	0.0349 (8)	0.0325 (8)	0.0383 (9)	−0.0020 (6)	0.0069 (7)	−0.0065 (7)
C7	0.0729 (17)	0.0515 (14)	0.0313 (10)	−0.0072 (11)	0.0128 (10)	−0.0039 (9)
C8	0.0368 (11)	0.0490 (13)	0.0746 (17)	0.0073 (9)	0.0170 (11)	−0.0152 (12)
C9	0.0433 (19)	0.0421 (18)	0.100 (3)	0.0182 (15)	0.000	0.000

Geometric parameters (Å, º) top

Co1—N5ⁱ	1.9601 (10)	N6—C7	1.481 (3)
Co1—N5	1.9601 (10)	N6—H6	0.9800
Co1—N6	1.9720 (16)	C7—C7ⁱⁱⁱ	1.486 (6)
Co1—N6ⁱ	1.9720 (16)	C7—H7A	0.9700
Co1—N6ⁱⁱ	1.9720 (16)	C7—H7B	0.9700
Co1—N6ⁱⁱⁱ	1.9720 (16)	C8—C9	1.501 (4)
Co1—Cl2	2.2513 (12)	C8—H8A	0.9700
Co1—Cl2ⁱ	2.2513 (12)	C8—H8B	0.9700
O4—N5	1.221 (4)	C9—C8ⁱⁱ	1.501 (4)
N5—O4ⁱⁱ	1.221 (4)	C9—H9A	0.9700
N6—C8	1.478 (3)	C9—H9B	0.9700

N5ⁱ—Co1—N5	180.0	O4ⁱⁱ—N5—Co1	121.76 (19)
N5ⁱ—Co1—N6	87.7 (3)	O4—N5—Co1	121.76 (19)
N5—Co1—N6	92.3 (3)	C8—N6—C7	111.64 (19)
N5ⁱ—Co1—N6ⁱ	92.3 (3)	C8—N6—Co1	118.86 (15)
N5—Co1—N6ⁱ	87.7 (3)	C7—N6—Co1	108.13 (13)
N6—Co1—N6ⁱ	180.0	C8—N6—H6	105.8
N5ⁱ—Co1—N6ⁱⁱ	87.7 (3)	C7—N6—H6	105.8
N5—Co1—N6ⁱⁱ	92.3 (3)	Co1—N6—H6	105.8
N6—Co1—N6ⁱⁱ	94.14 (10)	N6—C7—C7ⁱⁱⁱ	107.55 (16)
N6ⁱ—Co1—N6ⁱⁱ	85.86 (10)	N6—C7—H7A	110.2
N5ⁱ—Co1—N6ⁱⁱⁱ	92.3 (3)	C7ⁱⁱⁱ—C7—H7A	110.2
N5—Co1—N6ⁱⁱⁱ	87.7 (3)	N6—C7—H7B	110.2
N6—Co1—N6ⁱⁱⁱ	85.86 (10)	C7ⁱⁱⁱ—C7—H7B	110.2
N6ⁱ—Co1—N6ⁱⁱⁱ	94.14 (10)	H7A—C7—H7B	108.5
N6ⁱⁱ—Co1—N6ⁱⁱⁱ	180.0	N6—C8—C9	112.0 (2)
N5—Co1—Cl2	179.0 (5)	N6—C8—H8A	109.2
N6—Co1—Cl2	88.42 (7)	C9—C8—H8A	109.2
N6ⁱ—Co1—Cl2	91.58 (7)	N6—C8—H8B	109.2
N6ⁱⁱ—Co1—Cl2	88.42 (7)	C9—C8—H8B	109.2
N6ⁱⁱⁱ—Co1—Cl2	91.58 (7)	H8A—C8—H8B	107.9
N5ⁱ—Co1—Cl2ⁱ	179.0 (5)	C8—C9—C8ⁱⁱ	114.7 (3)
N6—Co1—Cl2ⁱ	91.58 (7)	C8—C9—H9A	108.6
N6ⁱ—Co1—Cl2ⁱ	88.42 (7)	C8ⁱⁱ—C9—H9A	108.6
N6ⁱⁱ—Co1—Cl2ⁱ	91.58 (7)	C8—C9—H9B	108.6
N6ⁱⁱⁱ—Co1—Cl2ⁱ	88.42 (7)	C8ⁱⁱ—C9—H9B	108.6
O4ⁱⁱ—N5—O4	116.4 (4)	H9A—C9—H9B	107.6

C8—N6—C7—C7ⁱⁱⁱ	172.3 (2)	Co1—N6—C8—C9	−54.6 (3)
Co1—N6—C7—C7ⁱⁱⁱ	39.7 (3)	N6—C8—C9—C8ⁱⁱ	67.3 (4)
C7—N6—C8—C9	178.5 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, −z+1; (iii) −x+1, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···Cl3	0.98	2.64	3.3671 (16)	131
C7—H7A···O4	0.97	2.28	2.929 (5)	124
C8—H8B···Cl2ⁱ	0.97	2.80	3.302 (4)	113

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The authors thank Dr Takashi Nemoto, Kyoto University, for making the program CAVITY available to the public.

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