Chlorido­bis­(ethane-1,2-di­amine)(4-fluoro­aniline)cobalt(III) dichloride monohydrate

SubbiahPandi, A.; AaminaNaaz, Y.; Mahalakshmi, C.M.; Anbalagan, K.

doi:10.1107/S2414314619003274

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 3| March 2019| x190327

https://doi.org/10.1107/S2414314619003274

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Chloridobis(ethane-1,2-diamine)(4-fluoroaniline)cobalt(III) dichloride monohydrate

A. SubbiahPandi,^a ^* Y. AaminaNaaz,^a C. Maharaja Mahalakshmi ^b and K. Anbalagan ^c

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^bDepartment of Chemistry, Chellammal Womens College, Chennai 600 032, India, and ^cDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 23 January 2019; accepted 7 March 2019; online 15 March 2019)

The hydrated title salt, [CoCl(C₆H₆FN)(C₂H₈N₂)₂]Cl₂·H₂O, comprises of one chloridobis(ethane-1,2-diamine)(4-fluoroaniline)cobalt(III) cation, two chloride counter-anions and a water molecule of crystallization. The Co^III ion has a distorted octahedral environment and is surrounded by four N atoms in the equatorial plane, with a fifth N atom and one Cl⁻ ligand occupying the axial positions. One of the methylene C groups in one of the ethane-1,2-diamine ligands is disordered over two set of sites in a 0.832 (10):0.168 (10) ratio. In the crystal, the complex cation, the two counter-anions and the water molecule of crystallization are linked via N—H⋯Cl, O—H⋯Cl and C—H⋯Cl hydrogen bonds, generating rings with R₄²(8), R₂¹(6), R₄²(10) and R₂²(6) graph-set motifs within a three-dimensional network.

Keywords: crystal structure; ethane-1,2-diamine; fluoroaniline ligand; cobalt(III) complex; hydrogen bonding; C—H⋯Cl interactions.

CCDC reference: 785047

Structure description

As a result of the excellent coordination ability of ligands with N-donating groups, such as simple amines (Mitzi, 1996 ; Deeth et al., 1984 ), cyanides (Wu et al., 2003 ; Shores et al., 2002 ), or N-heterocyclic rings (Hagrman et al., 1999 ; Willett et al., 2001 ), their respective transition-metal complexes have always been an active area in coordination chemistry. Ethylenediamine (en) has been used in innumerable coordination compounds as a ligand (Cullen & Lingafelter, 1970 ; Daniels et al., 1995 ; Jameson et al., 1982 ), because it not only chelates metal cations by two nitrogen atoms, but also donates hydrogen atoms to form N—H⋯X hydrogen bonds. In the vast majority of cases, en coordinates to a central metal ion as a bidentate ligand via the two N atoms, forming a five-membered chelate ring. This ligand has been widely used to prepare a number of cobalt(III) complexes (Bailar & Clapp, 1945 ; Bailar & Rollinson, 1946 ). Interestingly, mixed-ligand cobalt(III) complexes find potential applications in the fields of antitumor, antibacterial, antimicrobial, radiosenzitation and cytotoxicity activities (Sayed et al., 1992 ; Teicher et al., 1990 ; Arslan et al., 2009 ; Delehanty et al., 2008 ). It is well documented that cobalt(III)–chelate complexes can also function as efficient electron-transfer mediators in solar energy conversion schemes (Sapp et al., 2002 ). Complexes of cobalt are also useful for nutritional supplementation to provide cobalt in a form that effectively increases the bioavailability, for instance, vitamin B12 by microorganisms present in the gut. The structure determination of the title compound has been carried out against this background to ascertain the molecular conformation, binding modes and hydrogen-bonding interactions in the crystal structure.

The structural entities of the title salt are displayed in Fig. 1. The coordination environment around the Co^III atom is approximately octahedral and defined by one N-bound fluoroaniline ligand, one chloride ion and two ethylenediamine ligands. The angles subtended by the chelating en ligands deviate the most from 90° [N1—Co1—N2 = 85.23 (6)° and N3—Co1—N4 = 84.99 (6)°]. The N atoms N2, N3, N4 and N5 define the equatorial plane, and N1 and Cl1 the axial ligands. The Co—N bond lengths range from 1.9598 (14) to 2.0077 (13) Å, with the longest (Co1—N5) being the bond to the monodentate 4-fluoroaniline ligand. The methylene C2 atom in one of the five-membered en ligands is disordered over two sets of sites, with a refined occupancy ratio of 0.831 (10):0.168 (10). The chelate ring (Co1/N1/C1/C2/N2) adopts a twisted conformation on the C1—C2 bond with puckering parameters q₂ = 0.4012 (18) Å, and φ₂ = 92.2 (16)°. The chelate ring Co1/N1/C1/C2′/N2 with the minor contribution to the disorder at C2′ likewise exhibits a twisted conformation with puckering parameters q₂ = 0.149 (5) Å, and φ₂ = 19 (3)°. The chelate ring Co1/N3/C3/C4/N4 has puckering parameters q₂ = 0.4275 (15) Å, and φ₂ = 282.72 (15)°. The latter value indicates a conformation between a twisted and an envelope form.

Figure 1
The structural entities of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

The packing of the crystal structure is dominated by N—H⋯Cl, O—H⋯Cl and C—H⋯Cl hydrogen-bonding interactions (Table 1) between the complex cation, the two counter-anions and the water molecule of crystallization, thereby generating rings with $[R_{4}^{2}]$ (8), $[R_{2}^{1}]$ (6), $[R_{4}^{2}]$ (10) and $[R_{2}^{2}]$ (6) graph-set motifs. Within the three-dimensional network (Figs. 2 and 3), no π–π stacking interactions are observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯Cl2ⁱ	0.83 (1)	2.36 (1)	3.158 (2)	163 (3)
O1W—H2W⋯Cl1	0.83 (1)	2.47 (2)	3.175 (2)	144 (3)
N1—H1C⋯Cl3ⁱⁱ	0.83 (2)	2.76 (2)	3.5027 (16)	148.7 (17)
N1—H1D⋯Cl2	0.82 (2)	2.47 (2)	3.2421 (16)	156.7 (19)
N2—H2E⋯Cl3	0.84 (2)	2.60 (2)	3.4080 (16)	160.7 (18)
N2—H2F⋯Cl3ⁱⁱⁱ	0.91 (2)	2.70 (2)	3.5887 (16)	166 (2)
N3—H3C⋯O1W	0.88 (2)	2.18 (2)	2.989 (2)	152.2 (19)
N3—H3D⋯Cl2^iv	0.85 (2)	2.50 (2)	3.2791 (16)	154.0 (17)
N4—H4D⋯Cl2	0.87 (2)	2.61 (2)	3.4007 (17)	151.6 (18)
N4—H4C⋯Cl3ⁱⁱⁱ	0.84 (2)	2.56 (2)	3.3815 (16)	168.7 (17)
N5—H5A⋯Cl3	0.83 (2)	2.42 (2)	3.2345 (15)	168.6 (17)
N5—H5B⋯Cl3ⁱⁱ	0.90 (2)	2.38 (2)	3.2778 (15)	173.0 (17)
C4—H4A⋯Cl2^v	0.97	2.81	3.5148 (18)	130
Symmetry codes: (i) x, y+1, z; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x+2, -y+1, -z+2; (v) -x+1, -y+1, -z+2.

Figure 2
View of the three-dimensional hydrogen-bonded network of [Co^III(en)₂(p-FC₆H₄NH₂)Cl]Cl₂·H₂O, with hydrogen bonds indicated by dashed lines

Figure 3
Representative of all other hydrogen-bonding interactions, N—H⋯Cl hydrogen bonds are shown (dotted lines), generating an $[R_{4}^{2}]$ (8) ring motif.

Synthesis and crystallization

The complex was synthesized using dichloridobis(1,2-diaminoethane)cobalt(III) chloride according to a reported method (Bailar & Clapp, 1945). 2 g of trans-[Co^III(en)₂Cl₂]Cl were suspended in 3–4 drops of deionized water. 3 ml of 4-fluoroaniline were added dropwise over 20 min, and the final mixture was ground well for 30 min. Grinding was continued for half an hour, and a colour change was observed for every addition of amine; the colour was found to change from dull green to rosey red. The reaction mixture was set aside until no further colour change was observed. The product was allowed to stand overnight. Finally, the solid was washed 3–4 times with ethanol. The final complex was dissolved in 5–10 ml of deionized water and the solution heated to 343 K. The cobalt(III) complex was recrystallized from hot water by addition of a few drops of conc. HCl and cooling. The crystals were filtered, washed with ethanol and dried under vacuum.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The methylene group at C2 is disordered over two sets of sites and was refined with a 0.832 (10):0.168 (10) ratio.

Table 2
Experimental details

Crystal data
Chemical formula	[CoCl(C₆H₆FN)(C₂H₈N₂)₂]Cl₂·H₂O
M_r	414.62
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	8.1712 (6), 9.5435 (8), 11.9771 (10)
α, β, γ (°)	104.231 (4), 99.490 (4), 100.705 (4)
V (Å³)	867.57 (12)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.47
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with Eos detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.711, 0.810
No. of measured, independent and observed [I > 2σ(I)] reflections	15546, 3053, 2875
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.058, 1.12
No. of reflections	3053
No. of parameters	243
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.23
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS97 and SHELXL2014 (Sheldrick, 2008 , 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 785047

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619003274/wm4097sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619003274/wm4097Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Chloridobis(ethane-1,2-diamine)(4-fluoroaniline)cobalt(III) dichloride monohydrate top

Crystal data top

[CoCl(C₆H₆FN)(C₂H₈N₂)₂]Cl₂·H₂O	Z = 2
M_r = 414.62	F(000) = 428
Triclinic, P1	D_x = 1.587 Mg m⁻³
a = 8.1712 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5435 (8) Å	Cell parameters from 6556 reflections
c = 11.9771 (10) Å	θ = 1.8–25.0°
α = 104.231 (4)°	µ = 1.47 mm⁻¹
β = 99.490 (4)°	T = 293 K
γ = 100.705 (4)°	Prism, dark-red
V = 867.57 (12) Å³	0.25 × 0.20 × 0.15 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with Eos detector	3053 independent reflections
Radiation source: fine-focus sealed tube	2875 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and φ scan	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −9→9
T_min = 0.711, T_max = 0.810	k = −11→11
15546 measured reflections	l = −14→14

Refinement top

Refinement on F²	5 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0314P)² + 0.2678P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.040
3053 reflections	Δρ_max = 0.47 e Å⁻³
243 parameters	Δρ_min = −0.23 e Å⁻³

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.

Refinement. H atoms bonded to N and O atoms were freely refined. Other H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with 1.5U_eq(C) for methyl H and 1.2U_eq(C) for other H atoms.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.8028 (3)	0.2984 (2)	0.70155 (17)	0.0433 (4)
H1A	0.7069	0.2596	0.7323	0.052*
H1B	0.8789	0.2314	0.6994	0.052*
C2	0.7412 (5)	0.3087 (3)	0.5810 (2)	0.0366 (7)	0.831 (10)
H2A	0.8363	0.3268	0.5434	0.044*	0.831 (10)
H2B	0.6615	0.2167	0.5331	0.044*	0.831 (10)
C2'	0.677 (2)	0.2884 (16)	0.5948 (9)	0.0366 (7)	0.168 (10)
H2C	0.7164	0.2443	0.5251	0.044*	0.168 (10)
H2D	0.5688	0.2252	0.5932	0.044*	0.168 (10)
C3	0.8170 (2)	0.7410 (2)	0.97814 (14)	0.0355 (4)
H3A	0.8400	0.8379	1.0353	0.043*
H3B	0.8582	0.6730	1.0177	0.043*
C4	0.6297 (2)	0.6855 (2)	0.92613 (16)	0.0380 (4)
H4A	0.5701	0.6584	0.9842	0.046*
H4B	0.5839	0.7618	0.9003	0.046*
C5	1.07502 (19)	0.79981 (17)	0.68416 (13)	0.0260 (3)
C6	1.0343 (2)	0.91023 (19)	0.63617 (15)	0.0336 (4)
H6	0.9318	0.8913	0.5816	0.040*
C7	1.1462 (2)	1.0489 (2)	0.66945 (17)	0.0398 (4)
H7	1.1207	1.1239	0.6376	0.048*
C8	1.2952 (2)	1.0728 (2)	0.75043 (17)	0.0393 (4)
C9	1.3379 (2)	0.9665 (2)	0.80007 (17)	0.0404 (4)
H9	1.4395	0.9871	0.8558	0.049*
C10	1.2267 (2)	0.82760 (19)	0.76570 (15)	0.0330 (4)
H10	1.2539	0.7530	0.7974	0.040*
N1	0.89406 (19)	0.44838 (15)	0.77835 (13)	0.0274 (3)
N2	0.65522 (19)	0.43488 (16)	0.59361 (13)	0.0302 (3)
N3	0.90333 (18)	0.75159 (16)	0.87969 (12)	0.0270 (3)
N4	0.60849 (19)	0.55338 (17)	0.82415 (13)	0.0300 (3)
N5	0.96160 (18)	0.65309 (15)	0.64670 (12)	0.0264 (3)
O1W	0.8073 (3)	1.0395 (2)	0.8821 (2)	0.0898 (7)
F1	1.40512 (17)	1.20859 (13)	0.78300 (13)	0.0650 (4)
Cl1	0.63686 (5)	0.75092 (4)	0.66669 (4)	0.03357 (11)
Cl2	0.77375 (5)	0.36339 (5)	1.00298 (4)	0.03664 (11)
Cl3	0.77258 (5)	0.56575 (4)	0.37113 (3)	0.03353 (11)
Co1	0.78188 (2)	0.59758 (2)	0.73432 (2)	0.02174 (8)
H5A	0.907 (2)	0.641 (2)	0.5793 (18)	0.028 (5)*
H5B	1.027 (3)	0.586 (2)	0.6397 (17)	0.040 (5)*
H2E	0.658 (3)	0.459 (2)	0.5306 (19)	0.036 (5)*
H3C	0.907 (3)	0.841 (2)	0.8705 (18)	0.043 (6)*
H3D	1.004 (3)	0.744 (2)	0.9011 (17)	0.033 (5)*
H4C	0.510 (3)	0.535 (2)	0.7820 (18)	0.035 (5)*
H4D	0.622 (3)	0.478 (2)	0.8502 (18)	0.040 (5)*
H2F	0.544 (3)	0.417 (2)	0.5982 (19)	0.051 (6)*
H1D	0.891 (3)	0.446 (2)	0.846 (2)	0.040 (6)*
H1C	0.995 (3)	0.465 (2)	0.7716 (17)	0.034 (5)*
H2W	0.747 (3)	0.996 (3)	0.8157 (14)	0.087 (10)*
H1W	0.778 (4)	1.118 (2)	0.903 (3)	0.089 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0486 (11)	0.0300 (9)	0.0484 (11)	0.0114 (8)	0.0022 (9)	0.0098 (8)
C2	0.0345 (17)	0.0298 (11)	0.0397 (11)	0.0034 (11)	0.0061 (11)	0.0039 (8)
C2'	0.0345 (17)	0.0298 (11)	0.0397 (11)	0.0034 (11)	0.0061 (11)	0.0039 (8)
C3	0.0345 (9)	0.0432 (10)	0.0253 (8)	0.0069 (7)	0.0098 (7)	0.0032 (7)
C4	0.0317 (9)	0.0466 (10)	0.0364 (9)	0.0109 (8)	0.0153 (7)	0.0069 (8)
C5	0.0250 (8)	0.0295 (8)	0.0247 (8)	0.0055 (6)	0.0088 (6)	0.0084 (6)
C6	0.0323 (9)	0.0372 (9)	0.0325 (9)	0.0077 (7)	0.0035 (7)	0.0147 (7)
C7	0.0443 (11)	0.0340 (9)	0.0450 (10)	0.0078 (8)	0.0102 (8)	0.0190 (8)
C8	0.0371 (10)	0.0327 (9)	0.0433 (10)	−0.0024 (7)	0.0119 (8)	0.0079 (8)
C9	0.0259 (9)	0.0485 (11)	0.0409 (10)	0.0023 (8)	0.0007 (7)	0.0110 (8)
C10	0.0279 (9)	0.0378 (9)	0.0363 (9)	0.0094 (7)	0.0056 (7)	0.0156 (7)
N1	0.0255 (8)	0.0334 (7)	0.0262 (8)	0.0088 (6)	0.0064 (6)	0.0119 (6)
N2	0.0284 (8)	0.0317 (7)	0.0270 (7)	0.0041 (6)	0.0000 (6)	0.0082 (6)
N3	0.0217 (7)	0.0317 (8)	0.0252 (7)	0.0055 (6)	0.0041 (5)	0.0053 (6)
N4	0.0221 (7)	0.0367 (8)	0.0312 (7)	0.0053 (6)	0.0045 (6)	0.0117 (6)
N5	0.0266 (7)	0.0289 (7)	0.0234 (7)	0.0066 (6)	0.0048 (6)	0.0075 (6)
O1W	0.0933 (15)	0.0445 (10)	0.0991 (16)	0.0212 (10)	−0.0361 (12)	−0.0042 (10)
F1	0.0572 (8)	0.0422 (7)	0.0782 (9)	−0.0157 (6)	0.0012 (7)	0.0149 (6)
Cl1	0.0306 (2)	0.0346 (2)	0.0362 (2)	0.01223 (17)	0.00199 (17)	0.01167 (17)
Cl2	0.0293 (2)	0.0498 (3)	0.0349 (2)	0.00972 (18)	0.00575 (17)	0.02020 (19)
Cl3	0.0331 (2)	0.0377 (2)	0.0293 (2)	0.00967 (17)	0.00385 (16)	0.00964 (16)
Co1	0.01859 (12)	0.02502 (12)	0.02089 (12)	0.00481 (8)	0.00245 (8)	0.00680 (9)

Geometric parameters (Å, º) top

C1—C2'	1.472 (12)	C7—H7	0.9300
C1—N1	1.477 (2)	C8—F1	1.357 (2)
C1—C2	1.482 (3)	C8—C9	1.365 (3)
C1—H1A	0.9700	C9—C10	1.383 (3)
C1—H1B	0.9700	C9—H9	0.9300
C2—N2	1.492 (3)	C10—H10	0.9300
C2—H2A	0.9700	N1—Co1	1.9598 (14)
C2—H2B	0.9700	N1—H1D	0.82 (2)
C2'—N2	1.445 (12)	N1—H1C	0.83 (2)
C2'—H2C	0.9700	N2—Co1	1.9655 (14)
C2'—H2D	0.9700	N2—H2E	0.84 (2)
C3—N3	1.485 (2)	N2—H2F	0.91 (2)
C3—C4	1.494 (2)	N3—Co1	1.9512 (14)
C3—H3A	0.9700	N3—H3C	0.88 (2)
C3—H3B	0.9700	N3—H3D	0.85 (2)
C4—N4	1.484 (2)	N4—Co1	1.9613 (14)
C4—H4A	0.9700	N4—H4C	0.84 (2)
C4—H4B	0.9700	N4—H4D	0.87 (2)
C5—C10	1.383 (2)	N5—Co1	2.0077 (13)
C5—C6	1.384 (2)	N5—H5A	0.83 (2)
C5—N5	1.447 (2)	N5—H5B	0.90 (2)
C6—C7	1.384 (3)	O1W—H2W	0.825 (10)
C6—H6	0.9300	O1W—H1W	0.825 (10)
C7—C8	1.369 (3)	Cl1—Co1	2.2610 (4)

C2'—C1—N1	117.6 (6)	C1—N1—Co1	109.86 (11)
N1—C1—C2	108.71 (17)	C1—N1—H1D	105.6 (14)
N1—C1—H1A	109.9	Co1—N1—H1D	111.8 (14)
C2—C1—H1A	109.9	C1—N1—H1C	109.1 (13)
N1—C1—H1B	109.9	Co1—N1—H1C	110.6 (13)
C2—C1—H1B	109.9	H1D—N1—H1C	110 (2)
H1A—C1—H1B	108.3	C2'—N2—Co1	115.5 (5)
N2—C2—C1	107.1 (2)	C2—N2—Co1	109.53 (13)
N2—C2—H2A	110.3	C2'—N2—H2E	117.5 (14)
C1—C2—H2A	110.3	C2—N2—H2E	103.6 (13)
N2—C2—H2B	110.3	Co1—N2—H2E	112.5 (14)
C1—C2—H2B	110.3	C2'—N2—H2F	95.8 (11)
H2A—C2—H2B	108.6	C2—N2—H2F	118.2 (11)
N2—C2'—C1	110.1 (9)	Co1—N2—H2F	107.2 (13)
N2—C2'—H2C	109.6	H2E—N2—H2F	106 (2)
C1—C2'—H2C	109.7	C3—N3—Co1	111.09 (10)
N2—C2'—H2D	109.6	C3—N3—H3C	107.5 (14)
C1—C2'—H2D	109.6	Co1—N3—H3C	110.8 (14)
H2C—C2'—H2D	108.1	C3—N3—H3D	107.2 (13)
N3—C3—C4	107.41 (14)	Co1—N3—H3D	111.6 (13)
N3—C3—H3A	110.2	H3C—N3—H3D	108.5 (19)
C4—C3—H3A	110.2	C4—N4—Co1	108.62 (10)
N3—C3—H3B	110.2	C4—N4—H4C	108.8 (13)
C4—C3—H3B	110.2	Co1—N4—H4C	110.7 (13)
H3A—C3—H3B	108.5	C4—N4—H4D	109.1 (13)
N4—C4—C3	106.80 (14)	Co1—N4—H4D	109.6 (13)
N4—C4—H4A	110.4	H4C—N4—H4D	110.0 (19)
C3—C4—H4A	110.4	C5—N5—Co1	121.40 (10)
N4—C4—H4B	110.4	C5—N5—H5A	107.3 (13)
C3—C4—H4B	110.4	Co1—N5—H5A	103.8 (13)
H4A—C4—H4B	108.6	C5—N5—H5B	107.7 (13)
C10—C5—C6	120.28 (15)	Co1—N5—H5B	109.6 (12)
C10—C5—N5	119.46 (14)	H5A—N5—H5B	106.0 (18)
C6—C5—N5	120.23 (15)	H2W—O1W—H1W	105 (3)
C5—C6—C7	119.91 (16)	N3—Co1—N1	92.75 (6)
C5—C6—H6	120.0	N3—Co1—N4	84.99 (6)
C7—C6—H6	120.0	N1—Co1—N4	90.62 (7)
C8—C7—C6	118.35 (16)	N3—Co1—N2	176.62 (6)
C8—C7—H7	120.8	N1—Co1—N2	85.23 (6)
C6—C7—H7	120.8	N4—Co1—N2	92.31 (6)
F1—C8—C9	118.59 (17)	N3—Co1—N5	92.74 (6)
F1—C8—C7	118.41 (17)	N1—Co1—N5	91.00 (6)
C9—C8—C7	123.00 (16)	N4—Co1—N5	177.27 (6)
C8—C9—C10	118.52 (16)	N2—Co1—N5	90.01 (6)
C8—C9—H9	120.7	N3—Co1—Cl1	93.15 (5)
C10—C9—H9	120.7	N1—Co1—Cl1	174.09 (4)
C5—C10—C9	119.93 (15)	N4—Co1—Cl1	89.58 (5)
C5—C10—H10	120.0	N2—Co1—Cl1	88.86 (4)
C9—C10—H10	120.0	N5—Co1—Cl1	89.03 (4)

N1—C1—C2—N2	−48.3 (3)	N5—C5—C10—C9	178.51 (15)
N1—C1—C2'—N2	−6.3 (13)	C8—C9—C10—C5	−1.0 (3)
N3—C3—C4—N4	48.91 (19)	C2'—C1—N1—Co1	13.3 (8)
C10—C5—C6—C7	0.3 (2)	C2—C1—N1—Co1	36.3 (2)
N5—C5—C6—C7	−177.80 (15)	C1—C2'—N2—Co1	−3.8 (13)
C5—C6—C7—C8	−0.4 (3)	C1—C2—N2—Co1	38.2 (3)
C6—C7—C8—F1	179.91 (17)	C4—C3—N3—Co1	−32.55 (17)
C6—C7—C8—C9	−0.3 (3)	C3—C4—N4—Co1	−43.33 (17)
F1—C8—C9—C10	−179.23 (16)	C10—C5—N5—Co1	88.59 (17)
C7—C8—C9—C10	1.0 (3)	C6—C5—N5—Co1	−93.27 (16)
C6—C5—C10—C9	0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···Cl2ⁱ	0.83 (1)	2.36 (1)	3.158 (2)	163 (3)
O1W—H2W···Cl1	0.83 (1)	2.47 (2)	3.175 (2)	144 (3)
N1—H1C···Cl3ⁱⁱ	0.83 (2)	2.76 (2)	3.5027 (16)	148.7 (17)
N1—H1D···Cl2	0.82 (2)	2.47 (2)	3.2421 (16)	156.7 (19)
N2—H2E···Cl3	0.84 (2)	2.60 (2)	3.4080 (16)	160.7 (18)
N2—H2F···Cl3ⁱⁱⁱ	0.91 (2)	2.70 (2)	3.5887 (16)	166 (2)
N3—H3C···O1W	0.88 (2)	2.18 (2)	2.989 (2)	152.2 (19)
N3—H3D···Cl2^iv	0.85 (2)	2.50 (2)	3.2791 (16)	154.0 (17)
N4—H4D···Cl2	0.87 (2)	2.61 (2)	3.4007 (17)	151.6 (18)
N4—H4C···Cl3ⁱⁱⁱ	0.84 (2)	2.56 (2)	3.3815 (16)	168.7 (17)
N5—H5A···Cl3	0.83 (2)	2.42 (2)	3.2345 (15)	168.6 (17)
N5—H5B···Cl3ⁱⁱ	0.90 (2)	2.38 (2)	3.2778 (15)	173.0 (17)
C4—H4A···Cl2^v	0.97	2.81	3.5148 (18)	130

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

Acknowledgements

YA and ASP thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

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