Halogen-bonded co-crystal containing 1,3-di­iodo­perchloro­benzene and the photoproduct rtct-tetra­kis­(pyridin-4-yl)cyclo­butane resulting in a zigzag topology

Bosch, E.; Unruh, D.K.; Santana, C.L.; Groeneman, R.H.

doi:10.1107/S2056989023001408

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 79| Part 3| March 2023| Pages 212-215

https://doi.org/10.1107/S2056989023001408

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Halogen-bonded co-crystal containing 1,3-diiodoperchlorobenzene and the photoproduct rtct-tetrakis(pyridin-4-yl)cyclobutane resulting in a zigzag topology

Eric Bosch,^a Daniel K. Unruh,^b Carlos L. Santana ^c and Ryan H. Groeneman ^c ^*

^aMissouri State University, Department of Chemistry and Biochemistry, Springfield, MO 65897, USA, ^bTexas Tech University, Department of Chemistry and Biochemistry, Lubbock, TX 79409, USA, and ^cWebster University, Department of Biological Sciences, St. Louis, MO 63119, USA
^*Correspondence e-mail: ryangroeneman19@webster.edu

Edited by M. Zeller, Purdue University, USA (Received 3 February 2023; accepted 15 February 2023; online 21 February 2023)

The formation and crystal structure of a zigzag network held together by I⋯N halogen bonds is reported. In particular, the halogen-bond donor is 1,3-diiodoperchlorobenzene (C₆I₂Cl₄) while the acceptor is the photoproduct rtct-tetrakis(pyridin-4-yl)cyclobutane (TPCB). Curiously, within the resulting co-crystal (C₆I₂Cl₄)·(TPCB), the photoproduct accepts only two halogen bonds between neighbouring 4-pyridyl rings and as a result behaves as a bent two-connected node rather than the expected four-connected centre. In addition, the photoproduct, TPCB, is also found to engage in C—H⋯N hydrogen bonds, forming an extended zigzag chain.

Keywords: halogen bonding; organic solid state; co-crystal; photoproduct; cyclobutane; [2 + 2] cycloaddition reaction; zigzag network.

CCDC reference: 2236158

1. Chemical context

A continued focus for crystal engineers is the formation of molecular networks held together by non-covalent interactions (Vantomme & Meijer, 2019 ). Still today, research on these purely organic materials continues to lag behind related areas such as metal–organic frameworks as well as supramolecular coordinated solids. Co-crystallization has proven to be a successful approach in the formation of these extended organic solids (Gunawardana & Aakeröy, 2018 ). As in all types of network design, the components of these co-crystals must be carefully considered to ensure complementary supramolecular donor and acceptor sites that will allow for self-assembly of the multi-component solid. A highly utilized and well-established non-covalent interaction is halogen bonding, which is defined as the interaction between an electrophilic region on a halogen atom and a nucleophilic region on a different atom (Gilday et al., 2015 ). Overall, the strength and directionality of halogen bonds makes them an ideal supramolecular interaction, along with hydrogen bonds, as a driving force in the formation of co-crystals (Corpinot & Bučar, 2019 ).

A continued area of focus between our research groups has been in the design and formation of halogen-bonded molecular networks (Dunning et al., 2021 , 2022 ; Oburn et al., 2020 ; Sinnwell et al., 2020 ) that contain cyclobutane-based nodes generated from the [2 + 2] cycloaddition reaction between alkenes (Kole & Mir, 2022 ; Gan et al., 2018 ). Recently, we reported the ability to form a molecular salt with a square network topology based upon the tetraprotonated photoproduct rtct-tetrakis(pyridin-4-yl)cyclobutane and the sulfate anion (Santana et al., 2021b ). The rtct-isomer, which is the more stable thermodynamic product, is not directly observed from the solid-state [2 + 2] cycloaddition reaction, but rather forms after the photoreaction and an acid-catalysed isomerization reaction (Hill et al., 2012 ; Peedikakkal et al., 2010 ).

Herein, we report the solid-state crystal structure of a co-crystal held together by I⋯N halogen bonds that has a zigzag topology. In particular, the solid is based upon 1,3-diiodoperchlorobenzene (C₆I₂Cl₄) acting as the halogen-bond donor while the photoproduct rtct-tetrakis(pyridin-4-yl)cyclobutane (TPCB) behaves as the acceptor. Unexpectedly, the TPCB molecule is found to accept only two I⋯N halogen bonds, between neighbouring 4-pyridyl rings, which makes the photoproduct act as a bent two-connected node rather than a four-connected node as seen in the square network topology with the sulfate anion (Santana et al., 2021b).

2. Structural commentary

Crystallographic analysis revealed that the components of (C₆I₂Cl₄)·(TPCB) crystallize in the centrosymmetric monoclinic space group P2₁/c. The asymmetric unit contains a full molecule of both C₆I₂Cl₄ and TPCB (Fig. 1) although the crystals formed from a 2:1 solution of the two components. Notably, the TPCB molecule has an rtct-geometry, as expected since we first subjected the rctt-TPCB to an acid-catalysed isomerization. As a result of the isomerization reaction, the bond angles between neighbouring 4-pyridyl rings within TPCB are nearly perpendicular, with all four angles slightly obtuse at 93.64 (7), 96.05 (7), 96.37 (7) and 100.50 (7)°. These bond angles were measured from the centroids of the cyclobutane and the pyridine rings. As expected, the halogen-bond donor C₆I₂Cl₄ forms two crystallographically unique I⋯N halogen bonds with TPCB. The halogen-bond distances between I1⋯N4 and I2⋯N3ⁱ have values of 2.757 (4) and 2.909 (4) Å along with bond angles for C1—I1⋯N4 and C3—I2⋯N3ⁱ of 176.58 (15) and 172.73 (16)°, respectively [symmetry code: (i) 1 + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z]. Surprisingly, within (C₆I₂Cl₄)·(TPCB) only two adjacent 4-pyridyl rings are accepting these I⋯N halogen bonds. As a consequence of the observed formula and the lower than expected number of halogen bonds, TPCB behaves as a bent two-connecting node, resulting in a zigzag topology (Fig. 2). The pitch distance observed within (C₆I₂Cl₄)·(TPCB) is 20.51 (2) Å measured from the centroids of two nearest cyclobutane rings within the chain. Even though the I atoms on C₆I₂Cl₄ are found in the meta positions, rather than the para position, this halogen-bond donor acts as a nearly linear linker within (C₆I₂Cl₄)·(TPCB) (Fig. 2).

Figure 1
The labelled asymmetric unit of (C₆I₂Cl₄)·(TPCB). Displacement ellipsoids are drawn at the 50% probability level for non-hydrogen atoms while hydrogen atoms are shown as spheres of arbitrary size.

Figure 2
X-ray crystal structure of (C₆I₂Cl₄)·(TPCB) illustrating the zigzag network held together by I⋯N halogen bonds. Halogen bonds are represented by yellow dashed lines.

3. Supramolecular features

In addition to halogen bonding within (C₆I₂Cl₄)·(TPCB), the photoproduct TPCB is found to engage in a C—H⋯N hydrogen bond, resulting in a mono-periodic zigzag chain (Fig. 3). In particular, this C—H⋯N hydrogen bond has a C⋯N separation of 3.442 (7) Å and a C—H⋯N angle of 148°. It is important to note that the hydrogen-bond-accepting N atom does not accept halogen bonds. The donor H atom for this C—H⋯N hydrogen bond is in the 3-position on a pyridine ring that accepts a halogen bond.

Figure 3
X-ray crystal structure of (C₆I₂Cl₄)·(TPCB) illustrating the C—H⋯N hydrogen bonds between photoproducts forming a zigzag chain. Hydrogen bonds are represented by yellow dashed lines.

These different types of non-covalent interactions were also investigated and visualized by a Hirshfeld surface analysis (Spackman et al., 2021 ) mapped over d_norm (Fig. 4). The darkest red spots on the Hirshfeld surface represent I⋯N halogen bonds while the faint red spots indicate the C—H⋯N interactions. The adjacent halogen bond accepting 4-pyridyl groups within TPCB generates the two-connecting node and the bent geometry required for a zigzag topology.

Figure 4
Hirshfeld surface of (C₆I₂Cl₄)·(TPCB) mapped over d_norm illustrating the I⋯N halogen bonds (darkest red spots) and the C—H⋯N hydrogen bonds (faint red spots).

4. Database survey

A search of the Cambridge Crystallographic Database, Version 2022.3.0 Build 364, (Groom et al., 2016 ) using Conquest (Bruno et al., 2002 ) for structures containing tetrakis(pyridin-4-yl)cyclobutane in which one pyridyl N atom is within the van der Waals radius of a halogen atom revealed a total of four structures. Two of these structures correspond to the rtct-isomer. One of these, refcode RULHAK, is our earlier report of the tetrahedral network formed between 1,4-diiodoperchlorobenzene and rctt-TPCB (Oburn et al., 2020), in which all four pyridyl N atoms are halogen-bond acceptors. In the other structure, refcode EKUJOM (Santana et al., 2021a ), a chlorine atom ortho to a hydrogen-bonded phenol has a geometry-enforced close contact to the N atom.

5. Synthesis and crystallization

Materials and general methods The solvents such as reagent grade ethanol, dimethyl sulfoxide, chloroform, and toluene were all purchased from Sigma-Aldrich Chemical (St. Louis, MO, USA) and used as received. In addition, resorcinol (res), trans-1,2-bis(pyridin-4-yl)ethylene (BPE), concentrated sulfuric acid, and sodium hydroxide pellets were also purchased from Sigma-Aldrich and were used without additional purification. The [2 + 2] cycloaddition reaction was conducted in an ACE Glass photochemistry cabinet using UV-radiation from a 450 W medium-pressure mercury lamp. The occurrence of both the [2 + 2] cycloaddition reaction along with the acid-catalysed isomerization reaction were confirmed by using ¹H Nuclear Magnetic Resonance Spectroscopy on a Bruker Avance 400 MHz spectrometer with dimethyl sulfoxide (DMSO-d₆) as the solvent. The halogen-bond donor 1,3-diiodoperchlorobenzene (C₆I₂Cl₄) was synthesized utilizing a previously published method (Reddy et al., 2006 ).

Synthesis and crystallization The formation of the halogen-bond acceptor rtct-tetrakis(pyridin-4-yl)cyclobutane (TPCB) was achieved by using a previously published approach (Santana et al., 2021a). In particular, the co-crystal 2(res)·2(BPE) undergoes a [2 + 2] cycloaddition reaction to yield rctt-tetrakis(pyridin-4-yl)cyclobutane as previously reported (MacGillivray et al., 2000 ). The rctt-photoproduct was removed from the template by means of a base extraction with 0.2 M sodium hydroxide solution along with chloroform as the solvent. The conversion from rctt- to the rtct-isomer was achieved by heating 100 mg of the rctt-photoproduct in a 10 mL beaker with 2.0 mL of dimethyl sulfoxide along with two drops of sulfuric acid. The resulting solution was heated on a hot plate for one hour at 373 K (Peedikakkal et al., 2010). The complete upfield shift of the cyclobutane in the ¹H NMR spectra from 4.86 ppm for the rctt-isomer to 3.86 ppm for the rtct-isomer confirms the quantitative yield for this isomerization reaction. The separation of the photoproduct from the sulfate salt was achieved by a base extraction with 0.2 M sodium hydroxide and again chloroform in three 10.0 mL aliquots. Removal of the chloroform yielded pure TPCB (Fig. 1 in the supporting information).

The formation of (C₆I₂Cl₄)·(TPCB) was achieved by dissolving 64.0 mg of C₆I₂Cl₄ in 2.0 mL of toluene and then combined with a 2.0 mL ethanol solution containing 25.0 mg of TPCB (2:1 molar equivalent). Within three days, single crystals suitable for X-ray diffraction were formed upon loss of some of the solvent by slow evaporation.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Intensity data were corrected for Lorentz, polarization, and background effects using CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ ). A numerical absorption correction was applied based on a Gaussian integration over a multifaceted crystal and followed by a semi-empirical correction for absorption applied using the program SCALE3 ABSPACK. The program SHELXT (Sheldrick, 2015a ) was used for the initial structure solution while SHELXL (Sheldrick, 2015b ) for the refinement of the structure. Both programs were utilized within the OLEX2 software (Dolomanov et al., 2009 ). Hydrogen atoms bound to carbon atoms were located in the difference-Fourier map and were geometrically constrained using the appropriate AFIX commands.

Table 1
Experimental details

Crystal data
Chemical formula	C₂₄H₂₀N₄·C₆Cl₄I₂
M_r	832.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.0779 (1), 31.1307 (3), 9.3360 (1)
β (°)	90.986 (1)
V (Å³)	2928.57 (5)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	20.46
Crystal size (mm)	0.20 × 0.14 × 0.14

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ )
T_min, T_max	0.077, 0.552
No. of measured, independent and observed [I > 2σ(I)] reflections	41005, 6078, 5833
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.115, 1.06
No. of reflections	6078
No. of parameters	361
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −1.59
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ ), SHELXT2018/2 (Sheldrick, 2015a), SHELXL2018/3 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009).

Supporting information

CCDC reference: 2236158

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023001408/zl5042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023001408/zl5042Isup2.hkl

NMR spectrum. DOI: https://doi.org/10.1107/S2056989023001408/zl5042sup3.docx

Supporting information file. DOI: https://doi.org/10.1107/S2056989023001408/zl5042Isup4.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.41.99a (Rigaku OD, 2021); cell refinement: CrysAlis PRO 1.171.41.99a (Rigaku OD, 2021); data reduction: CrysAlis PRO 1.171.41.99a (Rigaku OD, 2021); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Olex2 1.3-ac4 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.3-ac4 (Dolomanov et al., 2009).

1,3-Diiodo-2,4,5,6-tetrachlorobenzene–rtct-1,2,3,4-tetrakis(pyridin-4-yl)cyclobutane top

Crystal data top

C₂₄H₂₀N₄·C₆Cl₄I₂	F(000) = 1608
M_r = 832.10	D_x = 1.887 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.0779 (1) Å	Cell parameters from 33737 reflections
b = 31.1307 (3) Å	θ = 2.8–77.2°
c = 9.3360 (1) Å	µ = 20.45 mm⁻¹
β = 90.986 (1)°	T = 100 K
V = 2928.57 (5) Å³	Irregular, clear colourless
Z = 4	0.20 × 0.14 × 0.14 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	6078 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	5833 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.065
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.5°, θ_min = 2.8°
ω scans	h = −12→12
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2021)	k = −39→37
T_min = 0.077, T_max = 0.552	l = −11→11
41005 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0613P)² + 12.119P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
6078 reflections	Δρ_max = 1.29 e Å⁻³
361 parameters	Δρ_min = −1.59 e Å⁻³
0 restraints

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	0.76302 (3)	0.50879 (2)	0.21577 (3)	0.02318 (10)
I2	1.14818 (3)	0.64897 (2)	0.04465 (4)	0.02936 (11)
Cl1	0.98841 (11)	0.58501 (4)	0.27061 (12)	0.0250 (2)
Cl2	0.73773 (12)	0.49167 (4)	−0.14080 (13)	0.0281 (2)
Cl3	0.88684 (12)	0.54236 (4)	−0.37433 (12)	0.0290 (2)
Cl4	1.07924 (13)	0.61572 (4)	−0.28903 (13)	0.0327 (3)
C1	0.8680 (4)	0.54128 (15)	0.0555 (5)	0.0204 (9)
C2	0.9583 (4)	0.57339 (15)	0.0918 (5)	0.0209 (9)
C3	1.0255 (5)	0.59739 (15)	−0.0116 (5)	0.0217 (9)
C4	1.0010 (5)	0.58722 (16)	−0.1554 (5)	0.0247 (10)
C5	0.9136 (5)	0.55427 (16)	−0.1959 (5)	0.0236 (9)
C6	0.8470 (5)	0.53186 (16)	−0.0900 (5)	0.0225 (9)
N1	0.6291 (5)	0.61957 (16)	−0.2002 (5)	0.0330 (10)
N2	1.0786 (4)	0.73533 (15)	0.3749 (5)	0.0307 (9)
N3	0.3362 (4)	0.78121 (14)	0.5891 (5)	0.0273 (9)
N4	0.3606 (4)	0.53628 (13)	0.5702 (4)	0.0236 (8)
C7	0.7200 (5)	0.64543 (17)	−0.1411 (6)	0.0281 (10)
H7	0.780112	0.659565	−0.202606	0.034*
C8	0.7319 (5)	0.65292 (16)	0.0056 (5)	0.0237 (9)
H8	0.798244	0.671855	0.042088	0.028*
C9	0.6457 (5)	0.63240 (15)	0.0980 (5)	0.0218 (9)
C10	0.5535 (5)	0.60444 (16)	0.0385 (6)	0.0263 (10)
H10	0.494626	0.588964	0.097843	0.032*
C11	0.5480 (6)	0.59925 (18)	−0.1101 (6)	0.0307 (11)
H11	0.483249	0.580267	−0.149585	0.037*
C12	0.6517 (4)	0.64127 (14)	0.2565 (5)	0.0198 (9)
H12	0.714761	0.620999	0.305369	0.024*
C13	0.6797 (5)	0.68819 (15)	0.3058 (5)	0.0207 (9)
H13	0.633720	0.708195	0.237435	0.025*
C14	0.5868 (4)	0.67970 (15)	0.4330 (5)	0.0202 (9)
H14	0.638296	0.666329	0.513896	0.024*
C15	0.5189 (4)	0.64356 (15)	0.3393 (5)	0.0191 (9)
H15	0.448070	0.656435	0.276453	0.023*
C16	0.8187 (5)	0.70430 (15)	0.3320 (5)	0.0209 (9)
C17	0.8615 (5)	0.74167 (17)	0.2657 (6)	0.0280 (10)
H17	0.803580	0.757245	0.203397	0.034*
C18	0.9901 (6)	0.75586 (18)	0.2917 (6)	0.0315 (11)
H18	1.016950	0.781868	0.247481	0.038*
C19	1.0362 (5)	0.69957 (17)	0.4377 (5)	0.0264 (10)
H19	1.097139	0.684339	0.497523	0.032*
C20	0.9090 (5)	0.68310 (16)	0.4216 (5)	0.0241 (9)
H20	0.883834	0.657762	0.470998	0.029*
C21	0.5012 (4)	0.71508 (15)	0.4889 (5)	0.0220 (9)
C22	0.5111 (5)	0.75683 (16)	0.4375 (6)	0.0255 (10)
H22	0.574784	0.763737	0.367313	0.031*
C23	0.4277 (5)	0.78824 (16)	0.4892 (6)	0.0281 (10)
H23	0.435614	0.816476	0.451741	0.034*
C24	0.3279 (5)	0.74149 (18)	0.6397 (6)	0.0296 (11)
H24	0.264454	0.735785	0.711315	0.036*
C25	0.4073 (5)	0.70759 (16)	0.5935 (5)	0.0253 (10)
H25	0.397271	0.679697	0.633192	0.030*
C26	0.4656 (5)	0.60485 (15)	0.4143 (5)	0.0197 (9)
C27	0.5467 (5)	0.57869 (15)	0.5005 (5)	0.0215 (9)
H27	0.639630	0.583583	0.506637	0.026*
C28	0.4896 (5)	0.54561 (15)	0.5768 (5)	0.0222 (9)
H28	0.545384	0.528619	0.637202	0.027*
C29	0.2839 (5)	0.56031 (16)	0.4856 (5)	0.0250 (10)
H29	0.192019	0.553694	0.478941	0.030*
C30	0.3309 (5)	0.59454 (16)	0.4064 (5)	0.0227 (9)
H30	0.271976	0.610824	0.347239	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02362 (16)	0.02170 (16)	0.02419 (17)	−0.00011 (10)	−0.00097 (11)	0.00065 (10)
I2	0.02659 (17)	0.02932 (18)	0.03203 (18)	−0.00289 (12)	−0.00289 (13)	0.00211 (12)
Cl1	0.0244 (5)	0.0292 (6)	0.0214 (5)	−0.0035 (4)	−0.0020 (4)	−0.0017 (4)
Cl2	0.0307 (6)	0.0270 (6)	0.0265 (6)	−0.0042 (4)	−0.0058 (5)	−0.0025 (4)
Cl3	0.0320 (6)	0.0358 (6)	0.0192 (5)	0.0029 (5)	−0.0026 (4)	−0.0009 (4)
Cl4	0.0387 (7)	0.0331 (6)	0.0266 (6)	−0.0027 (5)	0.0065 (5)	0.0064 (5)
C1	0.020 (2)	0.022 (2)	0.019 (2)	0.0017 (17)	0.0051 (17)	0.0050 (17)
C2	0.017 (2)	0.023 (2)	0.023 (2)	0.0023 (17)	−0.0003 (17)	0.0022 (17)
C3	0.020 (2)	0.019 (2)	0.026 (2)	−0.0025 (16)	−0.0021 (18)	−0.0001 (17)
C4	0.025 (2)	0.024 (2)	0.025 (2)	0.0029 (18)	0.0005 (19)	0.0030 (18)
C5	0.022 (2)	0.027 (2)	0.022 (2)	0.0053 (18)	−0.0003 (18)	0.0024 (18)
C6	0.022 (2)	0.025 (2)	0.021 (2)	0.0045 (17)	−0.0042 (17)	0.0017 (18)
N1	0.038 (2)	0.037 (3)	0.023 (2)	0.005 (2)	−0.0017 (18)	−0.0079 (18)
N2	0.027 (2)	0.036 (2)	0.030 (2)	−0.0076 (18)	−0.0003 (18)	0.0024 (18)
N3	0.0214 (19)	0.028 (2)	0.032 (2)	0.0048 (16)	−0.0061 (17)	−0.0074 (17)
N4	0.028 (2)	0.022 (2)	0.0208 (19)	0.0000 (16)	0.0049 (16)	−0.0003 (15)
C7	0.032 (3)	0.028 (3)	0.024 (2)	0.005 (2)	0.002 (2)	−0.0005 (19)
C8	0.022 (2)	0.026 (2)	0.023 (2)	0.0006 (18)	0.0019 (18)	−0.0057 (18)
C9	0.023 (2)	0.020 (2)	0.023 (2)	0.0046 (17)	−0.0008 (18)	−0.0027 (17)
C10	0.025 (2)	0.027 (2)	0.027 (2)	−0.0009 (19)	−0.0014 (19)	−0.0063 (19)
C11	0.033 (3)	0.031 (3)	0.028 (3)	−0.001 (2)	−0.002 (2)	−0.006 (2)
C12	0.019 (2)	0.018 (2)	0.023 (2)	0.0008 (16)	−0.0005 (17)	−0.0028 (17)
C13	0.023 (2)	0.018 (2)	0.021 (2)	−0.0014 (17)	−0.0016 (17)	0.0011 (17)
C14	0.020 (2)	0.019 (2)	0.022 (2)	−0.0003 (16)	−0.0013 (17)	−0.0009 (17)
C15	0.017 (2)	0.021 (2)	0.020 (2)	0.0015 (16)	−0.0003 (17)	−0.0016 (17)
C16	0.021 (2)	0.024 (2)	0.018 (2)	−0.0017 (17)	0.0014 (17)	−0.0050 (17)
C17	0.027 (2)	0.026 (2)	0.032 (3)	−0.0012 (19)	0.001 (2)	0.004 (2)
C18	0.034 (3)	0.029 (3)	0.031 (3)	−0.006 (2)	0.001 (2)	0.004 (2)
C19	0.023 (2)	0.030 (3)	0.026 (2)	−0.0026 (19)	−0.0021 (19)	−0.0007 (19)
C20	0.025 (2)	0.025 (2)	0.022 (2)	−0.0043 (18)	0.0001 (18)	0.0004 (18)
C21	0.019 (2)	0.025 (2)	0.022 (2)	0.0010 (17)	−0.0064 (17)	−0.0031 (18)
C22	0.026 (2)	0.022 (2)	0.029 (2)	−0.0006 (18)	0.0001 (19)	−0.0024 (19)
C23	0.027 (2)	0.020 (2)	0.036 (3)	−0.0011 (18)	−0.004 (2)	−0.001 (2)
C24	0.025 (2)	0.033 (3)	0.030 (3)	0.005 (2)	0.001 (2)	−0.006 (2)
C25	0.026 (2)	0.025 (2)	0.024 (2)	0.0030 (19)	0.0011 (19)	−0.0022 (18)
C26	0.021 (2)	0.021 (2)	0.018 (2)	0.0007 (17)	0.0014 (17)	−0.0038 (16)
C27	0.022 (2)	0.023 (2)	0.020 (2)	0.0022 (17)	−0.0022 (17)	−0.0026 (17)
C28	0.025 (2)	0.021 (2)	0.021 (2)	0.0011 (17)	0.0006 (18)	−0.0026 (17)
C29	0.023 (2)	0.024 (2)	0.028 (2)	−0.0020 (18)	0.0007 (19)	−0.0029 (19)
C30	0.022 (2)	0.023 (2)	0.023 (2)	0.0022 (17)	−0.0024 (18)	0.0005 (18)

Geometric parameters (Å, º) top

I1—C1	2.106 (4)	C12—C15	1.558 (6)
I1—N4ⁱ	2.757 (4)	C13—H13	1.0000
I2—C3	2.088 (5)	C13—C14	1.548 (6)
I2—N3ⁱⁱ	2.909 (4)	C13—C16	1.504 (6)
Cl1—C2	1.730 (5)	C14—H14	1.0000
Cl2—C6	1.728 (5)	C14—C15	1.574 (6)
Cl3—C5	1.724 (5)	C14—C21	1.498 (6)
Cl4—C4	1.732 (5)	C15—H15	1.0000
C1—C2	1.390 (7)	C15—C26	1.498 (6)
C1—C6	1.402 (7)	C16—C17	1.390 (7)
C2—C3	1.404 (7)	C16—C20	1.392 (7)
C3—C4	1.397 (7)	C17—H17	0.9500
C4—C5	1.400 (7)	C17—C18	1.386 (8)
C5—C6	1.391 (7)	C18—H18	0.9500
N1—C7	1.332 (7)	C19—H19	0.9500
N1—C11	1.341 (8)	C19—C20	1.386 (7)
N2—C18	1.336 (7)	C20—H20	0.9500
N2—C19	1.332 (7)	C21—C22	1.390 (7)
N3—C23	1.340 (7)	C21—C25	1.391 (7)
N3—C24	1.327 (7)	C22—H22	0.9500
N4—C28	1.333 (6)	C22—C23	1.382 (7)
N4—C29	1.327 (7)	C23—H23	0.9500
C7—H7	0.9500	C24—H24	0.9500
C7—C8	1.392 (7)	C24—C25	1.397 (7)
C8—H8	0.9500	C25—H25	0.9500
C8—C9	1.391 (7)	C26—C27	1.398 (7)
C9—C10	1.383 (7)	C26—C30	1.397 (7)
C9—C12	1.506 (6)	C27—H27	0.9500
C10—H10	0.9500	C27—C28	1.383 (7)
C10—C11	1.397 (7)	C28—H28	0.9500
C11—H11	0.9500	C29—H29	0.9500
C12—H12	1.0000	C29—C30	1.385 (7)
C12—C13	1.556 (6)	C30—H30	0.9500

C1—I1—N4ⁱ	176.58 (15)	C21—C14—C13	120.1 (4)
C3—I2—N3ⁱⁱ	172.73 (16)	C21—C14—H14	109.7
C2—C1—I1	120.5 (3)	C21—C14—C15	118.1 (4)
C2—C1—C6	118.3 (4)	C12—C15—C14	86.5 (3)
C6—C1—I1	121.2 (4)	C12—C15—H15	109.8
C1—C2—Cl1	119.3 (4)	C14—C15—H15	109.8
C1—C2—C3	122.5 (4)	C26—C15—C12	120.9 (4)
C3—C2—Cl1	118.3 (4)	C26—C15—C14	118.1 (4)
C2—C3—I2	121.8 (4)	C26—C15—H15	109.8
C4—C3—I2	120.7 (4)	C17—C16—C13	120.1 (4)
C4—C3—C2	117.4 (4)	C17—C16—C20	117.4 (4)
C3—C4—Cl4	120.1 (4)	C20—C16—C13	122.5 (4)
C3—C4—C5	121.7 (4)	C16—C17—H17	120.5
C5—C4—Cl4	118.2 (4)	C18—C17—C16	119.0 (5)
C4—C5—Cl3	120.4 (4)	C18—C17—H17	120.5
C6—C5—Cl3	120.6 (4)	N2—C18—C17	124.2 (5)
C6—C5—C4	119.0 (5)	N2—C18—H18	117.9
C1—C6—Cl2	120.1 (4)	C17—C18—H18	117.9
C5—C6—Cl2	118.7 (4)	N2—C19—H19	117.8
C5—C6—C1	121.1 (5)	N2—C19—C20	124.4 (5)
C7—N1—C11	116.6 (5)	C20—C19—H19	117.8
C19—N2—C18	116.1 (5)	C16—C20—H20	120.6
C24—N3—C23	116.6 (4)	C19—C20—C16	118.9 (5)
C29—N4—C28	117.5 (4)	C19—C20—H20	120.6
N1—C7—H7	118.1	C22—C21—C14	121.5 (4)
N1—C7—C8	123.8 (5)	C22—C21—C25	116.9 (4)
C8—C7—H7	118.1	C25—C21—C14	121.6 (4)
C7—C8—H8	120.4	C21—C22—H22	120.2
C9—C8—C7	119.3 (5)	C23—C22—C21	119.6 (5)
C9—C8—H8	120.4	C23—C22—H22	120.2
C8—C9—C12	120.7 (4)	N3—C23—C22	123.9 (5)
C10—C9—C8	117.5 (5)	N3—C23—H23	118.1
C10—C9—C12	121.7 (4)	C22—C23—H23	118.1
C9—C10—H10	120.4	N3—C24—H24	118.2
C9—C10—C11	119.1 (5)	N3—C24—C25	123.7 (5)
C11—C10—H10	120.4	C25—C24—H24	118.2
N1—C11—C10	123.6 (5)	C21—C25—C24	119.3 (5)
N1—C11—H11	118.2	C21—C25—H25	120.3
C10—C11—H11	118.2	C24—C25—H25	120.3
C9—C12—H12	110.3	C27—C26—C15	121.8 (4)
C9—C12—C13	117.8 (4)	C30—C26—C15	121.1 (4)
C9—C12—C15	118.4 (4)	C30—C26—C27	117.0 (4)
C13—C12—H12	110.3	C26—C27—H27	120.4
C13—C12—C15	87.9 (3)	C28—C27—C26	119.1 (4)
C15—C12—H12	110.3	C28—C27—H27	120.4
C12—C13—H13	108.4	N4—C28—C27	123.5 (4)
C14—C13—C12	87.6 (3)	N4—C28—H28	118.2
C14—C13—H13	108.4	C27—C28—H28	118.2
C16—C13—C12	121.7 (4)	N4—C29—H29	118.3
C16—C13—H13	108.4	N4—C29—C30	123.5 (5)
C16—C13—C14	120.4 (4)	C30—C29—H29	118.3
C13—C14—H14	109.7	C26—C30—H30	120.4
C13—C14—C15	87.6 (3)	C29—C30—C26	119.3 (4)
C15—C14—H14	109.7	C29—C30—H30	120.4

I1—C1—C2—Cl1	2.5 (5)	C12—C13—C14—C21	−145.4 (4)
I1—C1—C2—C3	−176.7 (3)	C12—C13—C16—C17	127.3 (5)
I1—C1—C6—Cl2	−2.3 (5)	C12—C13—C16—C20	−52.6 (6)
I1—C1—C6—C5	178.0 (3)	C12—C15—C26—C27	45.7 (6)
I2—C3—C4—Cl4	3.3 (6)	C12—C15—C26—C30	−137.4 (5)
I2—C3—C4—C5	−176.5 (4)	C13—C12—C15—C14	−23.8 (3)
Cl1—C2—C3—I2	−4.6 (5)	C13—C12—C15—C26	−144.7 (4)
Cl1—C2—C3—C4	179.3 (4)	C13—C14—C15—C12	24.0 (3)
Cl3—C5—C6—Cl2	0.3 (6)	C13—C14—C15—C26	147.4 (4)
Cl3—C5—C6—C1	−180.0 (4)	C13—C14—C21—C22	−5.7 (7)
Cl4—C4—C5—Cl3	0.7 (6)	C13—C14—C21—C25	173.7 (4)
Cl4—C4—C5—C6	−178.2 (4)	C13—C16—C17—C18	179.9 (5)
C1—C2—C3—I2	174.6 (3)	C13—C16—C20—C19	178.6 (4)
C1—C2—C3—C4	−1.5 (7)	C14—C13—C16—C17	−125.0 (5)
C2—C1—C6—Cl2	179.0 (4)	C14—C13—C16—C20	55.1 (6)
C2—C1—C6—C5	−0.7 (7)	C14—C15—C26—C27	−58.1 (6)
C2—C3—C4—Cl4	179.5 (4)	C14—C15—C26—C30	118.8 (5)
C2—C3—C4—C5	−0.4 (7)	C14—C21—C22—C23	178.2 (4)
C3—C4—C5—Cl3	−179.5 (4)	C14—C21—C25—C24	−178.6 (4)
C3—C4—C5—C6	1.6 (7)	C15—C12—C13—C14	24.3 (3)
C4—C5—C6—Cl2	179.2 (4)	C15—C12—C13—C16	149.0 (4)
C4—C5—C6—C1	−1.1 (7)	C15—C14—C21—C22	−110.5 (5)
C6—C1—C2—Cl1	−178.8 (3)	C15—C14—C21—C25	68.9 (6)
C6—C1—C2—C3	2.0 (7)	C15—C26—C27—C28	174.5 (4)
N1—C7—C8—C9	0.4 (8)	C15—C26—C30—C29	−175.3 (4)
N2—C19—C20—C16	1.4 (8)	C16—C13—C14—C15	−149.8 (4)
N3—C24—C25—C21	0.1 (8)	C16—C13—C14—C21	88.8 (5)
N4—C29—C30—C26	0.0 (8)	C16—C17—C18—N2	1.7 (9)
C7—N1—C11—C10	1.0 (8)	C17—C16—C20—C19	−1.3 (7)
C7—C8—C9—C10	1.5 (7)	C18—N2—C19—C20	0.0 (8)
C7—C8—C9—C12	−177.2 (4)	C19—N2—C18—C17	−1.6 (8)
C8—C9—C10—C11	−2.2 (7)	C20—C16—C17—C18	−0.1 (7)
C8—C9—C12—C13	38.1 (6)	C21—C14—C15—C12	147.1 (4)
C8—C9—C12—C15	141.9 (5)	C21—C14—C15—C26	−89.5 (5)
C9—C10—C11—N1	0.9 (8)	C21—C22—C23—N3	0.7 (8)
C9—C12—C13—C14	145.5 (4)	C22—C21—C25—C24	0.8 (7)
C9—C12—C13—C16	−89.8 (5)	C23—N3—C24—C25	−0.6 (8)
C9—C12—C15—C14	−144.6 (4)	C24—N3—C23—C22	0.2 (8)
C9—C12—C15—C26	94.5 (5)	C25—C21—C22—C23	−1.2 (7)
C10—C9—C12—C13	−140.6 (5)	C26—C27—C28—N4	1.8 (7)
C10—C9—C12—C15	−36.8 (6)	C27—C26—C30—C29	1.7 (7)
C11—N1—C7—C8	−1.7 (8)	C28—N4—C29—C30	−0.9 (7)
C12—C9—C10—C11	176.6 (5)	C29—N4—C28—C27	−0.1 (7)
C12—C13—C14—C15	−24.0 (3)	C30—C26—C27—C28	−2.6 (6)

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

Funding information

RHG gratefully acknowledges financial support from Webster University in the form of various Faculty Research Grants.

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