Structure of Λ(δλλ)-[Co(en)3]I3(I)2

Kollitz, M.R.; Oliver, A.G.; Lappin, A.G.

doi:10.1107/S2056989021002826

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ISSN: 2056-9890

Volume 77| Part 4| April 2021| Pages 446-449

https://doi.org/10.1107/S2056989021002826

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Structure of Λ(δλλ)-[Co(en)₃]I₃(I)₂

Megan R. Kollitz,^a Allen G. Oliver ^a and A. Graham Lappin ^a ^*

^aUniversity of Notre Dame, Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, Notre Dame IN 46556, USA
^*Correspondence e-mail: alappin1@nd.edu

Edited by G. Diaz de Delgado, Universidad de Los Andes Mérida, Venezuela (Received 2 March 2021; accepted 15 March 2021; online 31 March 2021)

The structure of tris(ethane-1,2-diamine-κ²N,N')cobalt(III) bis(iodide) triiodide, [Co(C₂H₈N₂)₃]I₃(I)₂, at 120 K has orthorhombic (P2₁2₁2₁) symmetry. The diamine nitrogen atoms form N—H⋯I hydrogen bonds throughout the lattice, resulting in a three-dimensional network, which involves the iodide and all atoms in the triiodide anions.

Keywords: crystal structure; cobalt coordination; chiral coordination.

CCDC reference: 2070495

1. Chemical context

Significant information on the hydrogen bonding and other interactions that contribute to the chiral discriminations between metal-ion complexes has been obtained from the crystal structures of compounds containing a chiral complex cation and a chiral complex anion (Warren et al., 1994 ; Marusak & Lappin, 1989 ). For example, a comparison of the compounds Λ-[Co(en)₃]Δ-[Co(en)(ox)₂]I₂·3H₂O and Δ-[Co(en)₃]Δ-[Co(en)(ox)₂]I₂·H₂O reveals the importance of different helicities projected along the C₃ and C₂ axes of [Co(en)₃]³⁺ in discriminating with the pseudo-C₃ face of the Δ-[Co(en)(ox)₂]⁻ anion (Lappin et al., 1993 ).

As part of a study involving potential effects of non-chiral counter-ions, an attempt was made to grow crystals with [Co(en)₃]I₃ and Na[Co(edta)]. However, in the presence of I⁻, the mildly oxidizing [Co(edta)]⁻ was reduced and an unexpected product, [Co(en)₃]I₃(I)₂ was obtained. The structure of the corresponding cobalt(II) complex, [Co(en)₃]I₃I, has been reported (Du et al., 2007 ). The larger cobalt(II) complex supports an lel₃ geometry of the bidentate ligands around the cobalt center. The Co—N bond distances in [Co(en)₃]²⁺ average 2.28 Å, significantly longer than the 1.97 Å average in [Co(en)₃]³⁺ and consistent with the sluggish redox exchange between the complexes (Jolley et al., 1990 ). In [Co(en)₃]I₃I, the I⁻ ions are located along the quasi-C₂ axis of the [Co(en)₃]²⁺ complex ion with close hydrogen-bond contacts from N—H protons of 2.91 Å. The terminal iodine atoms of the I₃⁻ ions likewise form hydrogen bonds with N—H protons at 2.93 Å, resulting in an alternating chain of linear I₃⁻ ions at 90° to one another down the c-axis direction.

2. Structural commentary

The complex, [Co(en)₃](I₃)(I)₂ crystallizes as dark-red, rod-like crystals. The asymmetric unit of the primitive, acentric, orthorhombic space group P2₁2₁2₁ consists of one [Co(en)₃]³⁺ cation, two iodide anions and a triiodide anion (Fig. 1). The correct enantiomorph of the space group was determined by comparison of intensities of Friedel pairs of reflections, yielding a Flack x parameter of 0.017 (9) (Parsons et al., 2013 ) and a Hooft y parameter of 0.006 (8) (Hooft et al., 2008 ). Values close to zero indicate the correct enantiomorph of the space group. This determination allows an accurate assessment of the configuration of the cobalt cation.

Figure 1
Labeling scheme for [Co(en)₃]I₃(I)₂ with ellipsoids at the 50% probability level. Hydrogen atoms depicted as spheres of an arbitrary radius.

The cobalt center is located in a slightly distorted octahedral environment by the nitrogen atoms of three ethylene diamine ligands (see Table 1 for details). The ligands adopt a Λ(δλλ) lel ob ob (lelob₂) geometry about the cobalt center, Fig. 1. Bond distances and angles within the molecules are unexceptional.

Table 1
Selected geometric parameters (Å, °)

Co1—N1	1.964 (3)	Co1—N3	1.968 (3)
Co1—N5	1.967 (3)	Co1—N6	1.969 (3)
Co1—N4	1.968 (3)	Co1—N2	1.982 (3)

N1—Co1—N5	91.86 (14)	N4—Co1—N6	91.39 (13)
N1—Co1—N4	175.38 (14)	N3—Co1—N6	91.83 (13)
N5—Co1—N4	91.64 (14)	N1—Co1—N2	85.20 (13)
N1—Co1—N3	91.25 (13)	N5—Co1—N2	91.96 (14)
N5—Co1—N3	175.65 (14)	N4—Co1—N2	91.68 (13)
N4—Co1—N3	85.42 (14)	N3—Co1—N2	91.34 (15)
N1—Co1—N6	91.91 (13)	N6—Co1—N2	175.76 (13)
N5—Co1—N6	85.02 (13)

The amine hydrogen atoms were initially located from a difference-Fourier map and were refined freely. All of the amine hydrogen atoms are involved in hydrogen bonds to nearby iodine/triiodide moieties, Fig. 2. This interconnectivity results in a three-dimensional hydrogen-bonded network throughout the entire structure.

Figure 2
View down the b axis of [Co(en)₃]I₃(I)₂ showing the herringbone pattern, with ellipsoids at the 50% probability level.

3. Supramolecular features

The iodide ion I⁻(1) is hydrogen bonded to N—H protons from N4 on one [Co(en)₃]³⁺ ion at 2.77 Å, bridging to N—H protons on N4 and N5 from the two ligands with a λ-configuration on an adjacent cation with distances of 2.90 (5) and 2.95 (5) Å (Fig. 2, Table 2). The pairwise interactions create a hydrogen-bonded chain along the crystallographic a-axis direction, forming a layer with the complex cations separated by channels formed by I₃⁻ ions in an alternating herringbone pattern punctuated by I2⁻ ions. The iodide I2⁻ forms a hydrogen-bonded network bridging the layers with N—H protons from three separate cations at 2.79 (5), 2.80 (5) and 2.83 (5) Å. The I₃⁻ ion has a close N—H contact with N6 at 2.89 (5) Å.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯I2	0.87 (5)	2.83 (5)	3.598 (3)	149 (4)
N1—H1D⋯I2ⁱ	0.87 (5)	2.79 (5)	3.616 (3)	158 (4)
N2—H2C⋯I3ⁱⁱ	0.89 (5)	3.04 (5)	3.823 (3)	149 (4)
N2—H2D⋯I1ⁱⁱⁱ	0.80 (5)	3.02 (5)	3.756 (4)	154 (4)
N3—H3C⋯I2^iv	0.97 (5)	3.25 (5)	4.111 (3)	149 (4)
N3—H3C⋯I5^iv	0.97 (5)	3.08 (5)	3.586 (3)	114 (3)
N3—H3D⋯I1ⁱⁱⁱ	0.76 (5)	3.18 (5)	3.805 (4)	142 (5)
N4—H4C⋯I1	0.92 (5)	2.77 (5)	3.630 (3)	155 (4)
N4—H4D⋯I1^v	0.90 (5)	2.90 (5)	3.715 (3)	152 (4)
N5—H5C⋯I1^v	0.89 (5)	2.95 (5)	3.765 (3)	154 (4)
N5—H5C⋯I3ⁱⁱ	0.89 (5)	3.25 (5)	3.639 (3)	109 (3)
N5—H5D⋯I4ⁱⁱ	0.89 (5)	3.05 (5)	3.611 (3)	123 (4)
N6—H6C⋯I5	0.91 (5)	2.89 (5)	3.674 (3)	145 (4)
N6—H6D⋯I2^iv	0.95 (5)	2.80 (5)	3.684 (3)	157 (4)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

4. Database survey

A survey of Co(en)₃ coupled with iodine reveals 23 structures in the Cambridge Structural Database (CSD v5.42, November 2020; Groom et al., 2016 ). Predominantly these are Co(III) complexes. There are three reports of Co(en)₃I₃ (EDANEC, Matsuki et al., 2001 ; ENCOIH, Whuler et al., 1980 ; FIXLAI, Grant et al., 2019 ). EDANEC and FIXLAI are structural analyses of the Λ- and Δ-isomers, respectively. The structure determination by Whuler et al. is of the racemic cation species. A mixed Cl/I species was reported by Huang and co-workers (FAXMEX, Zhang et al., 2005 ). All of these reports also contain water of crystallization. There is one report of Co(en)₃ that has both an iodide and a triodide pair of counter-ions that crystallizes in the tetragonal space group I $[\overline{4}]$ 2d (HIQYUC, Du et al., 2007). However, that report is of the Co^II complex, Co(en)₃(I₃)I.

5. Synthesis and crystallization

Crystals were obtained from an attempt to co-crystallize optically active [Co(en)₃]³⁺ and the mildly oxidizing [Co(edta)]⁻ from Λ-[Co(en)₃]I₃ and Na[Co(edta)]. After storage at 283 K for two weeks, the deep-purple coloration of the [Co(edta)]⁻ ion had disappeared and dark-red well-formed crystals were recovered.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The structure was solved by dual-space methods (Sheldrick, 2015a ) and refined routinely (Sheldrick, 2015b ). Amine hydrogen atoms were refined freely and methylene hydrogen atoms were refined as riding on the carbon to which they are bonded with C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Co(C₂H₈N₂)₃]I₃(I)₂
M_r	873.74
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	120
a, b, c (Å)	8.7508 (12), 8.8333 (12), 25.982 (4)
V (Å³)	2008.4 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	8.54
Crystal size (mm)	0.28 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa X8 APEXII
Absorption correction	Numerical (SADABS; Krause et al., 2015 )
T_min, T_max	0.603, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	35617, 5024, 5023
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.012, 0.028, 1.33
No. of reflections	5024
No. of parameters	199
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.66
Absolute structure	Flack x determined using 2136 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013).
Absolute structure parameter	0.017 (9)
Computer programs: APEX3 and SAINT (Bruker, 2015 ), SHELXT2014/5 (Sheldrick, 2015a), SHELXL2018/3 (Sheldrick, 2015b), Mercury (Macrae et al., 2020 ), CIFTAB (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2070495

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002826/dj2023sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002826/dj2023Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: CIFTAB (Sheldrick, 2008) and publCIF (Westrip, 2010).

Tris(ethane-1,2-diamine-κ²N,N')cobalt(III) bis(iodide) triiodide top

Crystal data top

[Co(C₂H₈N₂)₃]I₃(I)₂	D_x = 2.890 Mg m⁻³
M_r = 873.74	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9680 reflections
a = 8.7508 (12) Å	θ = 2.4–28.4°
b = 8.8333 (12) Å	µ = 8.54 mm⁻¹
c = 25.982 (4) Å	T = 120 K
V = 2008.4 (5) Å³	Rod, dark red
Z = 4	0.28 × 0.15 × 0.10 mm
F(000) = 1576

Data collection top

Bruker Kappa X8 APEXII diffractometer	5024 independent reflections
Radiation source: fine-focus sealed tube	5023 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 8.33 pixels mm^-1	θ_max = 28.3°, θ_min = 1.6°
combination of ω and φ–scans	h = −11→11
Absorption correction: numerical (SADABS; Krause et al., 2015)	k = −11→11
T_min = 0.603, T_max = 1.000	l = −33→34
35617 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.012	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.028	w = 1/[σ²(F_o²) + (0.0073P)² + 1.9769P] where P = (F_o² + 2F_c²)/3
S = 1.33	(Δ/σ)_max = 0.001
5024 reflections	Δρ_max = 0.39 e Å⁻³
199 parameters	Δρ_min = −0.66 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 2136 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.017 (9)

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
I1	0.32971 (3)	0.22384 (3)	0.55282 (2)	0.01429 (5)
I2	0.69407 (3)	0.30959 (2)	0.22059 (2)	0.01325 (5)
I3	−0.13267 (3)	0.17300 (3)	0.01437 (2)	0.01367 (5)
I4	0.05242 (3)	0.28734 (2)	0.09775 (2)	0.01107 (5)
I5	0.22245 (3)	0.40722 (3)	0.18675 (2)	0.01307 (5)
Co1	0.32630 (5)	0.30665 (5)	0.36719 (2)	0.00693 (8)
N1	0.4364 (4)	0.4391 (3)	0.31911 (13)	0.0111 (6)
H1C	0.466 (6)	0.383 (5)	0.2936 (18)	0.013*
H1D	0.380 (6)	0.513 (5)	0.3077 (18)	0.013*
N2	0.4337 (4)	0.4219 (4)	0.42174 (12)	0.0119 (6)
H2C	0.374 (6)	0.453 (5)	0.4473 (19)	0.014*
H2D	0.500 (6)	0.370 (5)	0.4332 (19)	0.014*
N3	0.4917 (4)	0.1557 (3)	0.36466 (13)	0.0121 (6)
H3C	0.484 (6)	0.087 (5)	0.3358 (18)	0.015*
H3D	0.571 (6)	0.189 (6)	0.3664 (19)	0.015*
N4	0.2318 (4)	0.1713 (4)	0.41825 (12)	0.0122 (6)
H4C	0.248 (5)	0.217 (5)	0.4497 (19)	0.015*
H4D	0.129 (6)	0.168 (5)	0.4168 (18)	0.015*
N5	0.1500 (4)	0.4446 (3)	0.36922 (12)	0.0114 (6)
H5C	0.094 (6)	0.419 (5)	0.3963 (19)	0.014*
H5D	0.173 (6)	0.543 (5)	0.3687 (18)	0.014*
N6	0.2158 (4)	0.2066 (3)	0.31060 (12)	0.0109 (5)
H6C	0.261 (5)	0.236 (5)	0.2807 (19)	0.013*
H6D	0.227 (5)	0.100 (5)	0.3128 (18)	0.013*
C1	0.5641 (4)	0.5172 (4)	0.34653 (16)	0.0154 (7)
H1A	0.595861	0.608878	0.327383	0.018*
H1B	0.653317	0.448913	0.349678	0.018*
C2	0.5050 (5)	0.5596 (4)	0.39899 (16)	0.0158 (7)
H2A	0.589927	0.595429	0.421034	0.019*
H2B	0.428560	0.641804	0.396078	0.019*
C3	0.4761 (4)	0.0485 (4)	0.40885 (15)	0.0129 (7)
H3A	0.521899	0.092664	0.440276	0.016*
H3B	0.528980	−0.047957	0.401093	0.016*
C4	0.3078 (5)	0.0210 (4)	0.41678 (15)	0.0146 (7)
H4A	0.266124	−0.040706	0.388242	0.018*
H4B	0.290451	−0.033783	0.449508	0.018*
C5	0.0500 (4)	0.4213 (4)	0.32313 (15)	0.0135 (7)
H5A	0.089273	0.479960	0.293487	0.016*
H5B	−0.055557	0.455093	0.330595	0.016*
C6	0.0521 (4)	0.2540 (4)	0.31111 (15)	0.0135 (7)
H6A	−0.005054	0.196883	0.337647	0.016*
H6B	0.004415	0.234598	0.277189	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.00933 (10)	0.02215 (11)	0.01140 (10)	0.00063 (9)	−0.00073 (9)	−0.00018 (9)
I2	0.01308 (11)	0.01112 (9)	0.01555 (11)	−0.00011 (8)	−0.00068 (9)	−0.00056 (8)
I3	0.01745 (12)	0.01416 (10)	0.00939 (10)	0.00078 (8)	0.00012 (9)	−0.00136 (8)
I4	0.01061 (10)	0.01122 (9)	0.01138 (10)	0.00010 (8)	0.00211 (8)	0.00068 (8)
I5	0.01294 (11)	0.01450 (10)	0.01176 (11)	−0.00060 (8)	−0.00106 (9)	0.00081 (8)
Co1	0.0067 (2)	0.00784 (19)	0.00628 (19)	−0.00032 (16)	0.00029 (17)	0.00003 (15)
N1	0.0095 (14)	0.0099 (13)	0.0139 (15)	−0.0003 (11)	0.0011 (13)	0.0024 (11)
N2	0.0109 (15)	0.0144 (14)	0.0104 (14)	−0.0011 (12)	−0.0008 (12)	−0.0011 (11)
N3	0.0116 (15)	0.0110 (13)	0.0138 (15)	0.0019 (11)	0.0024 (13)	0.0024 (11)
N4	0.0083 (14)	0.0189 (14)	0.0095 (14)	−0.0023 (12)	0.0009 (12)	0.0023 (12)
N5	0.0108 (15)	0.0130 (14)	0.0104 (14)	0.0028 (11)	−0.0015 (12)	−0.0024 (11)
N6	0.0156 (14)	0.0080 (12)	0.0091 (13)	0.0005 (11)	−0.0008 (12)	−0.0004 (10)
C1	0.0100 (17)	0.0149 (16)	0.0212 (19)	−0.0073 (14)	−0.0008 (16)	0.0043 (14)
C2	0.0150 (18)	0.0125 (16)	0.020 (2)	−0.0049 (14)	−0.0044 (16)	−0.0013 (14)
C3	0.0147 (18)	0.0117 (15)	0.0124 (17)	0.0021 (13)	0.0000 (14)	0.0048 (13)
C4	0.0187 (19)	0.0112 (14)	0.0140 (17)	−0.0041 (14)	−0.0003 (15)	0.0048 (12)
C5	0.0103 (16)	0.0175 (16)	0.0127 (17)	0.0016 (13)	−0.0033 (14)	−0.0019 (13)
C6	0.0100 (16)	0.0178 (16)	0.0126 (16)	−0.0042 (13)	−0.0018 (14)	−0.0011 (13)

Geometric parameters (Å, º) top

I3—I4	2.8875 (4)	N5—H5C	0.89 (5)
I4—I5	2.9464 (4)	N5—H5D	0.89 (5)
Co1—N1	1.964 (3)	N6—C6	1.493 (5)
Co1—N5	1.967 (3)	N6—H6C	0.91 (5)
Co1—N4	1.968 (3)	N6—H6D	0.95 (5)
Co1—N3	1.968 (3)	C1—C2	1.505 (6)
Co1—N6	1.969 (3)	C1—H1A	0.9900
Co1—N2	1.982 (3)	C1—H1B	0.9900
N1—C1	1.494 (5)	C2—H2A	0.9900
N1—H1C	0.87 (5)	C2—H2B	0.9900
N1—H1D	0.87 (5)	C3—C4	1.507 (5)
N2—C2	1.490 (5)	C3—H3A	0.9900
N2—H2C	0.89 (5)	C3—H3B	0.9900
N2—H2D	0.80 (5)	C4—H4A	0.9900
N3—C3	1.495 (5)	C4—H4B	0.9900
N3—H3C	0.97 (5)	C5—C6	1.511 (5)
N3—H3D	0.76 (5)	C5—H5A	0.9900
N4—C4	1.486 (5)	C5—H5B	0.9900
N4—H4C	0.92 (5)	C6—H6A	0.9900
N4—H4D	0.90 (5)	C6—H6B	0.9900
N5—C5	1.498 (5)

I3—I4—I5	176.193 (11)	Co1—N5—H5D	115 (3)
N1—Co1—N5	91.86 (14)	H5C—N5—H5D	113 (4)
N1—Co1—N4	175.38 (14)	C6—N6—Co1	109.8 (2)
N5—Co1—N4	91.64 (14)	C6—N6—H6C	110 (3)
N1—Co1—N3	91.25 (13)	Co1—N6—H6C	107 (3)
N5—Co1—N3	175.65 (14)	C6—N6—H6D	112 (3)
N4—Co1—N3	85.42 (14)	Co1—N6—H6D	111 (3)
N1—Co1—N6	91.91 (13)	H6C—N6—H6D	107 (4)
N5—Co1—N6	85.02 (13)	N1—C1—C2	106.8 (3)
N4—Co1—N6	91.39 (13)	N1—C1—H1A	110.4
N3—Co1—N6	91.83 (13)	C2—C1—H1A	110.4
N1—Co1—N2	85.20 (13)	N1—C1—H1B	110.4
N5—Co1—N2	91.96 (14)	C2—C1—H1B	110.4
N4—Co1—N2	91.68 (13)	H1A—C1—H1B	108.6
N3—Co1—N2	91.34 (15)	N2—C2—C1	107.5 (3)
N6—Co1—N2	175.76 (13)	N2—C2—H2A	110.2
C1—N1—Co1	109.8 (2)	C1—C2—H2A	110.2
C1—N1—H1C	114 (3)	N2—C2—H2B	110.2
Co1—N1—H1C	107 (3)	C1—C2—H2B	110.2
C1—N1—H1D	104 (3)	H2A—C2—H2B	108.5
Co1—N1—H1D	113 (3)	N3—C3—C4	107.2 (3)
H1C—N1—H1D	110 (4)	N3—C3—H3A	110.3
C2—N2—Co1	109.5 (2)	C4—C3—H3A	110.3
C2—N2—H2C	107 (3)	N3—C3—H3B	110.3
Co1—N2—H2C	114 (3)	C4—C3—H3B	110.3
C2—N2—H2D	108 (4)	H3A—C3—H3B	108.5
Co1—N2—H2D	108 (3)	N4—C4—C3	107.3 (3)
H2C—N2—H2D	109 (5)	N4—C4—H4A	110.3
C3—N3—Co1	109.7 (2)	C3—C4—H4A	110.3
C3—N3—H3C	101 (3)	N4—C4—H4B	110.3
Co1—N3—H3C	113 (3)	C3—C4—H4B	110.3
C3—N3—H3D	106 (4)	H4A—C4—H4B	108.5
Co1—N3—H3D	115 (4)	N5—C5—C6	107.0 (3)
H3C—N3—H3D	111 (5)	N5—C5—H5A	110.3
C4—N4—Co1	109.7 (2)	C6—C5—H5A	110.3
C4—N4—H4C	110 (3)	N5—C5—H5B	110.3
Co1—N4—H4C	106 (3)	C6—C5—H5B	110.3
C4—N4—H4D	114 (3)	H5A—C5—H5B	108.6
Co1—N4—H4D	114 (3)	N6—C6—C5	106.7 (3)
H4C—N4—H4D	102 (4)	N6—C6—H6A	110.4
C5—N5—Co1	110.6 (2)	C5—C6—H6A	110.4
C5—N5—H5C	106 (3)	N6—C6—H6B	110.4
Co1—N5—H5C	107 (3)	C5—C6—H6B	110.4
C5—N5—H5D	105 (3)	H6A—C6—H6B	108.6

Co1—N1—C1—C2	−39.6 (3)	N3—C3—C4—N4	−49.3 (4)
Co1—N2—C2—C1	−37.5 (4)	Co1—N5—C5—C6	36.0 (3)
N1—C1—C2—N2	49.9 (4)	Co1—N6—C6—C5	40.5 (3)
Co1—N3—C3—C4	37.5 (3)	N5—C5—C6—N6	−49.1 (4)
Co1—N4—C4—C3	38.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···I2	0.87 (5)	2.83 (5)	3.598 (3)	149 (4)
N1—H1D···I2ⁱ	0.87 (5)	2.79 (5)	3.616 (3)	158 (4)
N2—H2C···I3ⁱⁱ	0.89 (5)	3.04 (5)	3.823 (3)	149 (4)
N2—H2D···I1ⁱⁱⁱ	0.80 (5)	3.02 (5)	3.756 (4)	154 (4)
N3—H3C···I2^iv	0.97 (5)	3.25 (5)	4.111 (3)	149 (4)
N3—H3C···I5^iv	0.97 (5)	3.08 (5)	3.586 (3)	114 (3)
N3—H3D···I1ⁱⁱⁱ	0.76 (5)	3.18 (5)	3.805 (4)	142 (5)
N4—H4C···I1	0.92 (5)	2.77 (5)	3.630 (3)	155 (4)
N4—H4D···I1^v	0.90 (5)	2.90 (5)	3.715 (3)	152 (4)
N5—H5C···I1^v	0.89 (5)	2.95 (5)	3.765 (3)	154 (4)
N5—H5C···I3ⁱⁱ	0.89 (5)	3.25 (5)	3.639 (3)	109 (3)
N5—H5D···I4ⁱⁱ	0.89 (5)	3.05 (5)	3.611 (3)	123 (4)
N6—H6C···I5	0.91 (5)	2.89 (5)	3.674 (3)	145 (4)
N6—H6D···I2^iv	0.95 (5)	2.80 (5)	3.684 (3)	157 (4)

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

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